CN113945644A - UPLC-MS/MS method for analyzing residual meperflutonazole and pyraclostrobin in grapes - Google Patents
UPLC-MS/MS method for analyzing residual meperflutonazole and pyraclostrobin in grapes Download PDFInfo
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- CN113945644A CN113945644A CN202010685104.6A CN202010685104A CN113945644A CN 113945644 A CN113945644 A CN 113945644A CN 202010685104 A CN202010685104 A CN 202010685104A CN 113945644 A CN113945644 A CN 113945644A
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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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- 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
Abstract
A UPLC-MS/MS method for analyzing the residual of chlorofluoromethrin and pyraclostrobin in grapes is characterized by comprising the following steps: the method adopts a dilution method to replace a QuEChERS method for purification, not only eliminates the matrix effect, but also solves the problem of low recovery rate of the chlorofluoromethride caused by the QuEChERS purification, samples are extracted by acetonitrile, an extracting solution is salted out, an upper layer organic phase is taken and diluted by 0.1 percent formic acid, and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection is carried out. The method can be used for residue analysis of the meperfluorfen and the pyraclostrobin in the grapes, and has the advantages of simplicity, rapidness, low cost and the like, the purification effect is good, the sensitivity is high, and the accuracy and the precision meet the requirements of a multi-residue analysis method.
Description
The technical field is as follows:
the invention belongs to the technical field of determination of pesticide residues in agricultural products, and relates to a method for determining residues of chlorofluoromethrin and pyraclostrobin in grapes.
Background art:
chlorofluoromethane (mefentrifluconazole) is a novel triazole fungicide developed by basf corporation under the development code BAS 750F. The variety is the 1 st triazole bactericide which is on the market 10 years after prothioconazole, and the unique isopropanol group in the molecule enables the triazole bactericide to be combined with a target flexibly from free state free rotation to form a combined state, well inhibits the transfer of the septoria, reduces the germ mutation, and delays the generation and development of resistance. Has the systemic conductivity, has the protection and treatment effects, and has higher activity compared with other azole bactericides; and has good environmental characteristics, low toxicity to mammals, bees and the like and high safety. The compound has wide application range of crops, has excellent activity on a series of diseases difficult to prevent, can be used for field crops such as corn, grains and soybean and economic crops such as pepper and grape, and can prevent and control diseases, rust diseases and the like caused by the septoria.
Pyraclostrobin (pyraclostatin) is a novel strobilurin fungicide, and shows good activity on almost all fungal diseases (ascomycetes, basidiomycetes, oomycetes and deuteromycetes); has the functions of protection, treatment and leaf penetration and conduction, and is widely used for preventing and treating diseases such as powdery mildew, rust disease, downy mildew and the like in crops such as fruits, vegetables, grains and the like.
The basf company plans to market single-dose chlorofluoromethrin and mixed-dose pyraclostrobin formulations in more than 50 countries in the future, including asian regions, and is expected to market in 2019. However, no residual analysis method for the chlorofluoromethane is reported at home and abroad, and no limit standard is established. Reported cucumber, watermelon, Chinese cabbage, tobacco, orange, soil, etcThe method for analyzing the residues of the pyraclostrobin in the sample matrix mainly adopts liquid chromatography and liquid chromatography-tandem mass spectrometry, and C is mostly adopted for pretreatment18Solid phase extraction or QuEChERS method purification with N-propyl ethylene diamine (PSA) or graphitized carbon as filler. The solid phase extraction method is time-consuming and high in cost, the QuEChERS method is simple to operate, but the chlorofluoromethane contains Cl and F atoms in the structure and is easy to PSA and NH2Adsorption, resulting in lower recovery.
The research improves a pretreatment method, adopts a dilution method to replace a QuEChERS method for purification, adopts ultra-high performance liquid chromatography-tandem mass spectrometry for detection, and can simultaneously detect the residual quantity of the meperflutonazole and the pyraclostrobin in the grape. The method has the advantages of high efficiency, high speed, low cost, simple and convenient operation, good purification effect, high sensitivity and the like, the accuracy and the precision both meet the requirements of a multi-residue analysis method, and the method can provide technical support for residue analysis of the chlorofluoromethoxyfen and the pyraclostrobin in other agricultural products.
The invention content is as follows:
the invention aims to disclose a UPLC-MS/MS method for analyzing the residue of trifloxystrobin and pyraclostrobin in grapes by adopting an improved QuEChERS method to process samples.
The invention aims to realize the following technical scheme, and the method for measuring the residues of the chlorofluoromethane and the pyraclostrobin in the grapes comprises the following steps of:
a. accurately weighing 5.00g (accurate to 0.01g) of the homogenized sample in a 50mL polypropylene plastic centrifuge tube, adding 20mL acetonitrile, oscillating for 5min on a vertical oscillator, adding 2.0g sodium chloride, oscillating for 5min on the vertical oscillator at 4000 rpm, centrifuging for 5min, and salting out and layering.
b. And (3) taking 1mL of supernatant into a 10mL polypropylene plastic centrifuge tube, adding 1mL of 0.1% formic acid, uniformly mixing by vortex, filtering through a 0.22-micron organic filter membrane into a sample injection vial, and detecting.
c. Preparation of standard working solutions: respectively weighing a proper amount of the standard products of the fluroxypyr and the pyraclostrobin, dissolving the standard products by using methanol, fixing the volume, preparing standard stock solution with the concentration of about 200 mu g/mL, and storing the standard stock solution at 4 ℃ for six months. Respectively sucking a proper amount of 2 pesticide standard stock solutions, diluting the stock solutions with methanol, respectively preparing a single standard solution with the concentration of 10 mu g/mL and a mixed standard working solution with the concentration of 10 mu g/mL and 1 mu g/mL, and preparing the standard working solution on site.
d. Preparing a matrix matching standard solution: and (3) treating the blank grape sample according to the same pretreatment method, and performing constant volume to obtain a blank sample matrix solution. Taking a proper amount of mixed standard working solution respectively, diluting with blank sample matrix solution, and preparing series matrix matching standard solutions with the concentrations of 0.0001. mu.g/mL, 0.001. mu.g/mL, 0.005. mu.g/mL, 0.0125. mu.g/mL and 0.05. mu.g/mL.
e. And (3) measuring the matrix matching standard solution and the sample to be tested by using an UPLC-MS/MS method, drawing a standard curve by using the concentration as a horizontal coordinate and the peak area of the quantitative ions as a vertical coordinate, and calculating the residual quantity of the target pesticide in the sample to be tested by using the standard curve.
The chromatographic conditions used in the UPLC-MS/MS assay were: a chromatographic column: acquisty UPLC HSS T3Column (2.1 mm. times.100 mm, 1.8 μm); mobile phase: acetonitrile-0.1% formic acid, volume ratio 90:10 isocratic elution. Flow rate: 0.2 mL/min; sample introduction amount: 2 mu L of the solution; column temperature: at 40 ℃.
The mass spectrometry conditions used were: ionization mode: electrospray positive ion ESI (+); capillary voltage: 3.0 Kv; ion source temperature: 150 ℃; desolventizing gas temperature: 450 ℃ and 500 ℃; desolventizing air flow rate: 900-; taper hole blowback air flow rate: 150L/hr; flow rate of atomizing gas: 7 bar. The detection mode is as follows: multiple reaction monitoring scans (MRM); the retention time and mass spectrum acquisition parameters for 2 pesticides are shown in table 1.
The method can be used for detecting the residual quantity of the meperfluthrin and the pyraclostrobin in the grapes, has the advantages of high efficiency, rapidness, simple and convenient operation, low cost, good purification effect, high sensitivity and the like, and both the accuracy and the precision meet the requirements of a multi-residue analysis method. Compared with the prior art, the method has the following excellent effects:
(1) the invention discloses a UPLC-MS/MS method for analyzing chlorofluoromethane residues in grapes, and no literature report of the chlorofluoromethane residue analysis method exists at present.
(2) The method adopts a dilution method to replace a QuEChERS method for purification, and solves the problem that the chlorofluoromethrin is purified by PSA or NH2Adsorption causes the problem of reduced recovery while eliminating matrix effects.
(3) The method can be used for synchronous analysis of the trifloxystrobin and the pyraclostrobin, and has the advantages of simplicity and convenience in operation, rapidness, low cost, good purification effect, high sensitivity and the like.
The sensitivity of the method of the invention:
the detection limit of the calculation method with the signal-to-noise ratio of 3 and the minimum addition concentration as the quantitative limit meet the requirement that the signal-to-noise ratio is greater than or equal to 10. The detection limit of the triflumizole and the pyraclostrobin is 0.00008 mg/kg. The limit of quantitation of cloflufen and pyraclostrobin is 0.001 mg/kg.
Linearity of the method of the invention:
to eliminate matrix effects, a standard curve was drawn using a matrix-matched standard working solution. Taking the concentration of the pesticide as a horizontal coordinate and the chromatographic peak area of the quantitative ions as a vertical coordinate, drawing a standard curve, and showing a linear equation and a correlation coefficient in table 2. The concentration of the fluroxypyr and the pyraclostrobin is in a good linear relation with the peak area within the concentration range of 0.0001-0.05 mu g/mL, and the correlation coefficients are all larger than 0.999.
The accuracy and precision of the method of the invention are as follows:
and performing standard addition recovery tests at three concentration levels, performing 5 parallel samples at each concentration level, performing sample pretreatment and UPLC-MS/MS analysis respectively, and calculating the recovery rate according to the standard addition amount and the measured value. The average recovery and Relative Standard Deviation (RSD) of trifloxystrobin and pyraclostrobin in grapes are shown in Table 3. As can be seen from table 3, the recovery of 2 pesticides in grapes was between 77.5% and 98.6% with a relative standard deviation of between 1.9% and 6.1%, meeting the requirements of residual analysis.
TABLE 1 Retention time and Mass Spectrometry acquisition parameters for Fluorofen-Epoxiconazole and pyraclostrobin
TABLE 2 Standard Curve, correlation coefficient and sensitivity of Chlorofloxacin and pyraclostrobin
Table 3 spiked recovery and relative standard deviation of trifloxystrobin and pyraclostrobin in grapes (n ═ 5)
Detailed Description
The invention is further illustrated by the following examples, which are illustrative only and are not meant to limit the scope of the invention in any way.
Example 1
400 g/L of the fluroxypyr-mepiquat chloride-pyraclostrobin suspending agent is diluted by 1500 times, the application is carried out for 3 times at intervals of 7 days, a grape sample collected 7 days after the last application is taken as a sample, and the method is adopted for carrying out sample pretreatment and ultra performance liquid chromatography-tandem mass spectrometry determination. The preparation method comprises the following steps:
1. instruments and reagents:
waters Acquity, USATMUPLC I-Class ultra-high performance liquid chromatograph, Xevo TQ-S triple quadrupole mass spectrometer; switzerland Mettler electronic balances (0.00001 g and 0.01g of sensible weights); turmagen high flux tissue grinder; a vortex mixer; a table-top high speed centrifuge; U.S. Milli-Q ultra pure Water apparatus.
The purity of the chlorofluoromethrin standard substance is 99.7 percent, and the purity of the pyraclostrobin standard substance is 99.9 percent; acetonitrile and formic acid are chromatographically pure, sodium chloride is analytically pure, and water is ultrapure water.
2. The sample pretreatment method comprises the following steps:
accurately weighing 5g (accurate to 0.01g) of well homogenized grape sample, adding 20mL of acetonitrile into a 50mL polypropylene plastic centrifuge tube, oscillating on a tissue grinder for 5min, adding 2g of sodium chloride, oscillating on the tissue grinder for 5min, and centrifuging at 4000 rpm for 5 min. Taking 1mL of the upper acetonitrile phase, adding 1mL of 0.1% formic acid into a 10mL polypropylene plastic centrifuge tube, uniformly mixing by vortex, filtering through a 0.22 μm organic filter membrane to a sample injection vial, and detecting.
3. Preparation of standard working solutions:
respectively absorbing appropriate amount of standard stock solutions of the fluroxypyr and the pyraclostrobin, diluting with methanol, preparing mixed standard working solution with the concentration of 10 mu g/mL and 1 mu g/mL, and preparing the mixed standard working solution on site.
4. Preparing a matrix matching standard solution:
the blank grape sample was treated in the same pretreatment manner (see step 2, "sample pretreatment method"), to obtain a blank sample matrix solution. Taking a proper amount of mixed standard working solution respectively, and preparing a series of matrix matching standard solutions with the concentrations of 0.0001. mu.g/mL, 0.001. mu.g/mL, 0.005. mu.g/mL, 0.0125. mu.g/mL and 0.05. mu.g/mL by using the blank sample matrix solution.
5. Measurement method
And (3) measuring the matrix matching standard solution with the series of concentrations, and drawing a standard curve by taking the concentration as an abscissa and the peak area of the quantitative ions as an ordinate. Then, the grape sample to be tested was measured to obtain the peak area of the quantitative ion of the pesticide, and the peak area was substituted into the standard curve to calculate the residual amounts of 2 pesticides as shown in table 4.
The chromatographic conditions used in the measurement by the UPLC-MS/MS method were: a chromatographic column: acquisty UPLC HSS T3Column (2.1 mm. times.100 mm, 1.8 μm); mobile phase: acetonitrile-0.1% formic acid, volume ratio 90:10 isocratic elution. Flow rate: 0.2 mL/min; sample introduction amount: 2 mu L of the solution; column temperature: at 40 ℃.
The mass spectrometry conditions used were: ionization mode: electrospray positive ion ESI (+); capillary voltage: 3.0 Kv; ion source temperature: 150 ℃; desolventizing gas temperature: 450 ℃ and 500 ℃; desolventizing air flow rate: 900-; taper hole blowback air flow rate: 150L/hr; flow rate of atomizing gas: 7 bar. The detection mode is as follows: multiple reaction monitoring scans (MRM); the retention time and mass spectrum acquisition parameters for 2 pesticides are shown in table 1.
Table 4 results of actually measuring residual amounts of chlorofluoromethrin and pyraclostrobin in samples
Claims (3)
1. A UPLC-MS/MS method for analyzing the residual of chlorofluoromethrin and pyraclostrobin in grapes is characterized by comprising the following steps: the method adopts a dilution method to replace a QuEChERS method for purification, not only eliminates the matrix effect, but also solves the problem of low recovery rate of the chlorofluoromethane caused by the QuEChERS purification, samples are extracted by acetonitrile, an extracting solution is salted out, an upper layer organic phase is taken and diluted by 0.1 percent formic acid, and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) is used for determination. The method comprises the following specific steps:
a. accurately weighing 5.00g (accurate to 0.01g) of the homogenized sample in a 50mL polypropylene plastic centrifuge tube, adding 20mL acetonitrile, oscillating for 5min on a vertical oscillator, adding 2.0g sodium chloride, oscillating for 5min on the vertical oscillator at 4000 rpm, centrifuging for 5min, and salting out and layering.
b. And (3) taking 1mL of supernatant into a 10mL polypropylene plastic centrifuge tube, adding 1mL of 0.1% formic acid, uniformly mixing by vortex, filtering through a 0.22-micron organic filter membrane into a sample injection vial, and detecting.
c. Preparation of standard working solutions: respectively weighing a proper amount of the standard products of the fluroxypyr and the pyraclostrobin, dissolving the standard products by using methanol, fixing the volume, preparing a standard stock solution with the concentration of about 200 mu g/mL, and storing the standard stock solution at 4 ℃ for six months. Respectively sucking a proper amount of 2 pesticide standard stock solutions, diluting the stock solutions with methanol, respectively preparing a single standard solution with the concentration of 10 mu g/mL and a mixed standard working solution with the concentration of 10 mu g/mL and 1 mu g/mL, and preparing the standard working solution on site.
d. Preparing a matrix matching standard solution: and (3) treating the blank grape sample according to the same pretreatment method to obtain a blank sample matrix solution. Taking a proper amount of mixed standard working solution respectively, diluting with blank sample matrix solution, and preparing series matrix matching standard solutions with the concentrations of 0.0001. mu.g/mL, 0.001. mu.g/mL, 0.005. mu.g/mL, 0.0125. mu.g/mL and 0.05. mu.g/mL.
e. And (3) measuring the matrix matching standard solution and the sample to be tested by using an UPLC-MS/MS method, drawing a standard curve by using the concentration as a horizontal coordinate and the peak area of the quantitative ions as a vertical coordinate, and calculating the residual quantity of the target pesticide in the sample to be tested by using the standard curve.
2. An assay according to claim 1, wherein the sample is a grape sample homogenized by a tissue homogenizer.
3. The UPLC-MS/MS method of chlofloxacin and pyraclostrobin residues in grapes of claim 1, characterized in that: the chromatographic conditions employed were: HSS T3The chromatographic column comprises a mobile phase and a chromatographic column, wherein the mobile phase consists of an organic phase and a water phase, the organic phase is acetonitrile, the water phase is 0.1% formic acid water solution, the volume ratio of the water phase to the organic phase is 0.1%, isocratic elution is adopted, the volume ratio of the organic phase to the water phase is 90:10, the flow rate is 0.2mL/min, the column temperature is 40 ℃, and the sample injection volume is 2 muL. The mass spectrometry conditions used were: electrospray positive ion ionization ESI (+), multiple reaction monitoring scan (MRM), capillary voltage: 3.0 Kv; ion source temperature: 150 ℃; desolventizing gas temperature: 450 ℃ and 500 ℃; desolventizing air flow rate: 900-; the taper hole voltage is 10-90V, and the collision energy is 10-90V.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115015425A (en) * | 2022-06-15 | 2022-09-06 | 山东省农业科学院 | Method for determining fluoride ether bacteria amide residue in salvia miltiorrhiza by combining solid phase extraction with UPLC-MS/MS |
| CN115201353A (en) * | 2022-06-16 | 2022-10-18 | 广州海关技术中心 | Method for detecting residual quantity of kresoxim-methyl in vegetables and fruits |
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2020
- 2020-07-16 CN CN202010685104.6A patent/CN113945644A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115015425A (en) * | 2022-06-15 | 2022-09-06 | 山东省农业科学院 | Method for determining fluoride ether bacteria amide residue in salvia miltiorrhiza by combining solid phase extraction with UPLC-MS/MS |
| CN115015425B (en) * | 2022-06-15 | 2024-02-23 | 山东省农业科学院 | Method for determining fluoroether bacteria amide residues in red sage root by combining solid phase extraction with UPLC-MS/MS |
| CN115201353A (en) * | 2022-06-16 | 2022-10-18 | 广州海关技术中心 | Method for detecting residual quantity of kresoxim-methyl in vegetables and fruits |
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Application publication date: 20220118 |