CN114609311A - Method for detecting oxygen-containing disinfection components in disinfection hand sanitizer - Google Patents
Method for detecting oxygen-containing disinfection components in disinfection hand sanitizer Download PDFInfo
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- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 30
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- 238000003795 desorption Methods 0.000 claims abstract description 29
- 238000001514 detection method Methods 0.000 claims abstract description 27
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- 238000004885 tandem mass spectrometry Methods 0.000 claims abstract description 14
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- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 18
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- 238000012544 monitoring process Methods 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 4
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- 238000010790 dilution Methods 0.000 claims description 3
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- 238000002552 multiple reaction monitoring Methods 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000344 soap Substances 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 13
- 230000008676 import Effects 0.000 abstract description 9
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- 238000011084 recovery Methods 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- 229960004592 isopropanol Drugs 0.000 description 13
- 239000011550 stock solution Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
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- 238000005516 engineering process Methods 0.000 description 5
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- 238000011012 sanitization Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
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- 230000005540 biological transmission Effects 0.000 description 4
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
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- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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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
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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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to a method for detecting oxygen-containing disinfection components in a disinfection hand sanitizer. The detection method comprises the steps of preparing a sample to be detected, and determining the content of oxygen-containing disinfection components in the sample to be detected by utilizing a purging trapping-gas chromatography/tandem mass spectrometry method. The detection method provided by the invention can realize adsorption and desorption of various oxygen-containing disinfection components by adopting a purging and trapping mode for sample injection, and can effectively separate the oxygen-containing disinfection components by using a specific chromatographic column and matching with a gas chromatography/tandem mass spectrometry, thereby effectively avoiding the influence of a large amount of solvent water and ethanol on the determination resolution of a target object. The method has high sensitivity, accuracy and stability, and can be used for batch determination of the import and export disinfection liquid soap samples.
Description
Technical Field
The invention belongs to the technical field of disinfection hand sanitizer detection, and particularly relates to a method for detecting oxygen-containing disinfection components in a disinfection hand sanitizer.
Background
The hand sanitizer is an indispensable daily consumable in life of people, and the supply and demand of domestic markets are short, so that the import quantity of the commodities is greatly increased. Some manufacturers intentionally add other sterilizing substances (alcohols such as methanol, epoxy substances) as sterilizing components instead of ethanol, which is expensive, by illegal blending or the like in order to reduce costs, which may expose people to a high risk of harmful substances such as methanol. In recent years, commercial products with the problems of over-standard methanol, epoxy compound detection and the like exist in the market, even no-clean liquid soap products using methanol to completely replace ethanol exist, and China or the American FDA notifies many disinfection liquid soap products containing methanol.
Such products containing excess methanol or other oxygen-containing hazardous components present a significant health safety risk, with the safety issues of various non-ethanol oxygen-containing sanitizing components in sanitizing handwash products being of increasing public concern. Therefore, a corresponding rapid and accurate screening and analyzing method is established for disinfection hand sanitizer products (hand washing gel, foam hand sanitizer, disinfection spray, no-clean hand sanitizer, disinfectant and the like), and analysis and detection of toxic and harmful substances are performed according to relevant product standards, so that the reduction or control of risks is very necessary.
At present, related reports aiming at the detection technology of toxic and harmful substances in epidemic prevention products such as food, daily cosmetics, disinfectant, mask protective clothing and the like are reported at home and abroad. For the analysis of oxygen-containing disinfection components, common targets are mainly methanol, isopropanol, ethylene oxide and the like, and the determination methods mainly comprise gas chromatography, gas chromatography-mass spectrometry, colorimetry, Raman spectroscopy and the like. The relevant standard GB 5009.266-2016 (determination of methanol in food) mainly adopts gas chromatography; GB 38850 & 2020 ' list of disinfectant raw materials and forbidden substances ', GB/T32610 & 2016 technical Specification for daily protective masks ' and American ASTM F2100-21 are mainly measured by headspace-gas chromatography. Related documents (Zhangzhui et al. purging trapping-gas chromatography-tandem mass spectrometry for determining the chemical analysis and measurement of ethylene oxide and propylene oxide [ J ] in the child protective mask, 12 months in 2021, volume 30, stage 12) report a method for determining the residual amounts of methanol and ethylene oxide in disinfectant and medical masks by using headspace sample injection gas chromatography-mass spectrometry. However, a method for simultaneously measuring the content of oxygen-containing disinfection components, particularly alcohol and epoxy compounds in a disinfection hand sanitizer sample is not reported.
Therefore, the development of a detection method capable of simultaneously detecting a plurality of oxygen-containing disinfection components in the disinfection hand sanitizer has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defect or deficiency that the existing method for detecting oxygen-containing disinfection components in the disinfection hand sanitizer can not detect a plurality of oxygen-containing disinfection components simultaneously, and provides a method for detecting the oxygen-containing disinfection components in the disinfection hand sanitizer. The detection method provided by the invention can realize adsorption and desorption of various oxygen-containing disinfection components by adopting a purging and trapping mode for sample injection, and can effectively separate the oxygen-containing disinfection components by using a specific chromatographic column and matching with a gas chromatography/tandem mass spectrometry, thereby effectively avoiding the influence of a large amount of solvent water and ethanol on the determination resolution of a target object. The method has high sensitivity, accuracy and stability, and can be used for batch determination of the import and export disinfection liquid soap samples.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for detecting oxygen-containing disinfection components in disinfection hand sanitizer comprises the following steps:
s1: diluting the disinfection hand sanitizer by using water as a solvent to obtain a sample to be tested;
s2: taking an internal standard substance as a reference, and determining the content of oxygen-containing disinfection components in the sample to be detected by utilizing a purging trapping-gas chromatography/tandem mass spectrometry method;
wherein, the conditions of purging and trapping in the step S2 are as follows: the blowing temperature is 40-50 ℃; the purging time is 5-10 min; the desorption temperature is 225-300 ℃, and the desorption time is 3-5 min;
the chromatographic column used in the gas chromatography is bonded/crosslinked polyethanol or dimethyl siloxane.
The inventor of the invention finds that the specific purging trapping-gas chromatography/tandem mass spectrometry method can be used for realizing the high-efficiency detection of a plurality of oxygen-containing disinfection components (10) in the disinfection hand sanitizer, and has high sensitivity, accuracy and stability. Specifically, the method comprises the following steps:
(1) water is used as a solvent, on one hand, all oxygen-containing disinfection components in the disinfection hand sanitizer have the characteristic of water solubility, and on the other hand, the oxygen-containing disinfection components have good stability in water and are beneficial to subsequent detection.
(2) By optimizing the sweeping and trapping conditions, the effective adsorption, trapping and desorption of the oxygen-containing disinfection components can be fully realized, and the repeatability and the reproducibility are good.
(3) By optimizing the chromatographic column, the high-efficiency separation of oxygen-containing disinfection components can be realized, and the interference of ethanol, water and the like with very close structures and properties on detection is avoided. In addition, the structures and properties of the components of the oxygen-containing disinfection component are very close, especially the retention time of the components such as methanol, ethylene oxide and the like is close, the collection ions of the mass spectrum are the same, and effective separation is difficult. Research shows that the separation effect is good when the specific chromatographic column is used for classification.
The detection method provided by the invention can realize adsorption and desorption of various oxygen-containing disinfection components by adopting a purging and trapping mode for sample injection, and can effectively separate the oxygen-containing disinfection components by using a specific chromatographic column and matching with a gas chromatography/tandem mass spectrometry, thereby effectively avoiding the influence of a large amount of solvent water and ethanol on the determination resolution of a target object. The 10 oxygen-containing disinfection components have a linear relation with the peak area within the concentration range of 4-250 ng/mL. The method has the limit of 0.005-0.0115 mu g/g, and can meet the limit requirements on substances such as methanol and the like in the regulations of hand sanitizer (GB/T34855) and American FDA medical monograph and related standards. The recovery rate of the sample is 85.1-116.0%, and the Relative Standard Deviation (RSD) is less than or equal to 5.3% (n is 6). The detection method is rapid, simple, accurate and reliable, and is suitable for batch analysis and determination of various oxygen-containing disinfection components in the import and export disinfection hand sanitizer.
Preferably, the oxygen-containing disinfection component is one or more of alcohol compounds or epoxy compounds.
More preferably, the alcohol compound is one or more of methanol, isopropanol, n-propanol, isobutanol or n-butanol.
More preferably, the epoxy compound is one or more of 2, 3-epoxybutane, 2-vinyl oxirane, epichlorohydrin, ethylene oxide and propylene oxide.
Preferably, the dilution in S1 is 25-50 times.
Preferably, the conditions for purging and trapping in S2 are: purging with high-purity helium gas at a flow rate of 40 mL/min; the temperature of the dry purging is 50 ℃, the time of the dry purging is 1min, and the flow rate of the dry purging is 100 mL/min.
Preferably, the conditions of purging and trapping in S2 are that the six-way valve temperature is 150 ℃, the transfer line temperature is 150 ℃, the sample fixation area temperature is 90 ℃, the standby flow rate is 5mL/min, the purging preparation temperature is 35 ℃, the baking time is 0.5min, and the transfer line and valve temperature is 150 ℃.
Preferably, the purge temperature in S2 is 45 ℃; the purging time is 9 min; the desorption temperature is 250 ℃, and the desorption time is 3 min.
Preferably, the column is an INNOWAX column or a DB-624UI column.
The INNOWAX chromatographic column uses bonded/cross-linked polyethanol as a stationary phase, and the DB-624UI chromatographic column uses dimethyl siloxane as a stationary phase.
Preferably, the length of the chromatography column is 60 m; the inner diameter is 0.25 and the film thickness is 0.25-1.40 μm.
Preferably, the column flow rate of the chromatographic column in S2 is 1.0mL/min, the sample injection temperature is 240-250 ℃, and the split ratio is 10: 1; and heating to 50 ℃ at a heating rate of 5 ℃/min by taking 30-35 ℃ as an initial temperature, and then heating to 250 ℃ at a heating rate of 15 ℃/min.
Preferably, the mass spectral conditions in S2 are: electron bombardment of the ion source (EI) with an energy of 70eV, negative ion mode (MRM) with multiple reaction monitoring, solvent delay of 2 min.
Preferably, the internal standard is diethyl ether. The internal standard peak time is between the targets detected and the ion formed is also in the lower molecular weight range, similar to the target compounds.
Compared with the prior art, the invention has the following beneficial effects:
the detection method provided by the invention can realize adsorption and desorption of various (10) oxygen-containing disinfection components by adopting a purging and trapping mode for sample injection, and can realize effective separation of the oxygen-containing disinfection components by utilizing a specific chromatographic column and matching with a gas chromatography/tandem mass spectrometry, thereby effectively avoiding the influence of a large amount of solvent water and ethanol on the determination resolution of a target object. The method has high sensitivity, accuracy and stability, and can be used for batch determination of the import and export disinfection liquid soap samples.
Drawings
FIG. 1 is a diagram of contour lines and response surfaces of isopropanol recovery rates affected by interaction of four factors;
FIG. 2 is a multi-reaction monitoring total ion current chromatogram;
FIG. 3 is a data statistics plot of test results for a sample of a foam soap, sanitizing spray, and leave-in soap;
FIG. 4 is a multi-reaction monitoring chromatogram of a sample of a sanitizing liquid soap.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the examples below, generally according to conditions conventional in the art or as recommended by the manufacturer; the raw materials, reagents and the like used are those commercially available from conventional markets and the like unless otherwise specified. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
(1) The main instrument and reagent information used in each example is as follows:
gas chromatography-mass spectrometry/mass spectrometer: agilent 7890B-7000C;
MassHunter software data processing System, Agilent technologies, USA;
purging and trapping concentrator: AQUATek 100, Takrama instruments USA;
DB-624UI capillary column 30m by 0.25mm (inside diameter) by 1.40 μm (thickness) chromatography column, Agilent technologies, USA;
an ultra-pure water machine: Milli-Q type, Millipore corporation, USA;
adjustable pipettes, prandtl, germany; 10 μ L microsyringe;
methanol, isopropanol, n-propanol, 2, 3-butylene oxide, 2-vinyl ethylene oxide, isobutanol, n-butanol and epichlorohydrin standard substances are all purchased from Dr. Ehrenstontorfer GmbH company of Germany, and the purity is more than or equal to 98 percent;
ethylene oxide was purchased from Shanghai' an spectral laboratory science and technology, Inc. at 50000 mg/L;
the propylene oxide stock solution is purchased from Shanghai' an spectral experiment science and technology Co., Ltd, 1000 mg/L;
anhydrous ether, analytically pure, 99%, purchased from Guangzhou chemical reagent works;
the water is ultrapure water.
(2) The information on the standard working solution used in each example is as follows:
transferring alcohol standard substances (methanol, isopropanol, n-propanol, isobutanol and n-butanol) with certain mass, 2, 3-epoxybutane, 2-vinyl ethylene oxide, epichlorohydrin, an ethylene oxide stock solution with certain volume and an epoxy propane stock solution into a 10mL brown volumetric flask, diluting with ultrapure water to a constant volume, and preparing the standard stock solution of the oxygen-containing substance with the concentration of 10 mu g/mL.
Internal standard stock solution: transferring a certain amount of diethyl ether into a 10mL brown volumetric flask which is filled with 2mL of ultrapure water in advance, diluting with the ultrapure water to a constant volume to scale, and preparing into a diethyl ether standard stock solution with the concentration of 10 mug/mL.
Working solution: in the experiment, the standard stock solution of the oxygen-containing substance and the ether standard internal standard stock solution are prepared at the temperature below 4 ℃ to prepare a standard working solution of 10 oxygen-containing compounds (namely 10 oxygen-containing disinfection components) with target substance concentrations of 1.0, 2.0, 5.0, 10.0, 20.0 and 50.0ng/mL, wherein the internal standard concentration is 5.0 ng/mL.
Example 1 optimization of purge trap conditions
In this embodiment, the purging and trapping conditions are optimized, and the specific process is as follows:
1. pretreatment of the sample:
a hand sanitizer sample containing 5ng/mL isopropanol (1.0 g) is weighed and placed in a 50mL volumetric flask pre-filled with distilled water, and the volume is determined by using the distilled water. And (3) filling 40mL of the diluent into a purge bottle, adding 20 mu L of 10 mu g/mL diethyl ether standard stock solution below the solution surface, sealing by an upper screw cap, and automatically injecting by placing a purge and capture injector.
2. Measurement by purge trap-gas chromatography/tandem mass spectrometry:
the specific conditions are as follows:
(1) purging and trapping conditions
An orthogonal test is utilized to set 3 levels for the sweeping temperature (A, DEG C), the sweeping time (B, min), the desorption temperature (C, DEG C) and the desorption time (D, min) in sweeping and trapping conditions as variables, the recovery rate of a certain hand sanitizer sample containing 5ng/mL of isopropanol is used as a response value, and 29 experiments with 4 factors and 3 levels are carried out according to the design principle of a Box-Behnken center combined experiment.
The conditions for each set of experiments are shown in table 1.
Table 1 design of quadrature conditions
The other conditions are as follows: purging with high-purity helium gas at a flow rate of 40mL/min, a six-way valve temperature of 150 ℃, a transmission line temperature of 150 ℃, a sample fixing area temperature of 90 ℃, a standby flow rate of 5mL/min, a purging preparation temperature of 35 ℃, a baking time of 0.5min, a transmission line and valve temperature of 150 ℃, and a dry purging temperature, time and gas flow rate of 20 ℃, 1min and 100mL/min respectively.
Desorbing with high-purity helium at 245 deg.C, and desorption gas flow rate of 300 mL/min.
(2) Chromatographic conditions
DB-624 Quartz capillary columns (60m × 0.25mm, 1.40 μm); carrier gas: high purity helium gas; column flow rate: 1.0 mL/min; sample inlet temperature: 240 ℃; the split ratio is 10: 1; initial temperature: 35 deg.C (keeping for 3min), heating to 50 deg.C at 5 deg.C/min (keeping for 0min), and rapidly heating to 250 deg.C at 15 deg.C/min.
(3) Conditions of Mass Spectrometry
Electron impact ion source (EI), energy 70 eV; transmission line temperature: 250 ℃; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; multiple reactions were monitored for negative ion mode (MRM) with solvent delay of 2 min.
FIG. 1 is a graph of iso-propanol recovery contour lines and response surface for four-factor interaction. Fitting to obtain a regression model equation:
Recovery＝94.6+1.67A+2.67B+0.8333C+2.17D-2.25AB-1.25AD+0.5BC+0.75BD-2CD-9.92A2-2.17B2-0.925C2-2.43D2
the results of the above experiments were analyzed for variance, and the results are shown in Table 2. As can be seen from Table 2, the F value of the model is 17.44, and the model probability P value is 0.0023 < 0.05, which indicates that each influence factor has a significant influence on the recovery rate of the target substance. According to the comprehensive experiment result, the fitting degree of the model is good, the adjustment correlation coefficient is 0.8915, the correlation between the predicted value and the measured value is good, and 89.15% of response value change of the model can be analyzed. The recovery rate of isopropanol content in the hand sanitizer can be analyzed by using the model. From the F value, the first order term B of the model had a very significant effect, and the C effect was not significant. The influence sequence of single factors on the recovery rate is B & gtD & gtA & gtC, and the purging time & gt, namely the desorption time & gt the purging temperature & gt the desorption temperature. Second order term A2、B2、D2Significant influence, C2The effect was not significant.
Longer purging and desorption time and proper purging and desorption temperature can effectively improve the repeatability and reproducibility of analysis. In the range of room temperature to 45 ℃, the recovery rates of the target substance and the internal standard substance are increased along with the increase of the purging temperature, and when the purging temperature reaches more than 45 ℃, the recovery rate is not changed greatly. Within a certain range, the higher the desorption temperature is, the better the effect is, and the higher the desorption temperature is, the better the target object can be sent into the gas chromatographic column, so that a sharp chromatographic peak can be obtained. Desorption is more complete with longer desorption times, but desorption temperatures are too high and longer times can reduce adsorbent life. Therefore, in order to obtain a good peak shape, the shorter the desorption time, the better after the desorption temperature is determined. And (3) obtaining the optimal parameters by combining the actual sample treatment and analysis efficiency and analyzing a response surface model, wherein the purging temperature is 45 ℃, the purging time is 9min, the desorption temperature is 250 ℃, and the desorption time is 3min are selected as test parameters.
In order to further verify the reliability of data, the optimal conditions are adopted to carry out a blank sample labeling recovery experiment containing the matrix, the experiment is repeated for 3 times, the total recovery rate is 91.2 percent and is equivalent to a theoretical value, so that the sample blowing temperature is 45 ℃, the blowing time is 9min, the desorption temperature is 250 ℃, and the desorption time is 3 min.
TABLE 2 analysis of variance results of Box-Benhnken center combination design
Example 2 optimization of chromatographic conditions
In this example, the chromatographic conditions (chromatographic column) are optimized by the following specific procedures:
1. pretreatment of the sample:
weighing 1.0g of a certain liquid soap blank sample, adding a proper amount of standard stock solution and internal standard solution of 10 oxygen-containing compounds, placing the mixture into a 50mL volumetric flask pre-filled with distilled water, adding the standard solution, and fixing the volume by using the distilled water. A purge bottle was filled with 40mL of the above diluent, 20. mu.L of 10. mu.g/mL ether standard stock solution was added to the solution below the surface of the solution, and the solution was sealed with a screw cap to prepare a sample of a diluent solution having a final internal standard concentration of 5.0ng/mL and 10 kinds of oxygen-containing compounds each having a concentration of 10.0 ng/mL. And automatically injecting the sample when the sample is placed in a blowing and trapping sample injector.
2. Purge trap-gas chromatography/tandem mass spectrometry assay:
(1) purging and trapping conditions
The optimal purge trap conditions obtained were optimized as in example 1.
(2) Chromatographic conditions
Experiments were performed with several chromatographic columns with different stationary phases: DB-5MS UI (60 m.times.0.25 mm, 0.25 μm) column using (5% phenyl) methylpolysiloxane as a stationary phase, INNOWAX (60 m.times.0.25 mm, 0.25 μm) column using bonded/crosslinked polyethanol as a stationary phase, Agilent DB-624UI type (60 m.times.0.25 mm, 1.4 μm) using 6% cyanopropylbenzene, 94% dimethylsiloxane as a stationary phase, DB-17MS (60 m.times.0.25 mm.times.0.25 μm) using (50% -phenyl) -methylpolysiloxane as a stationary phase.
The other conditions are as follows: carrier gas: high purity helium gas; column flow rate: 1.0 mL/min; sample inlet temperature: 240 ℃; the split ratio is 10: 1; initial temperature: 35 deg.C (maintaining for 3min), heating to 50 deg.C at 5 deg.C/min (maintaining for 0min), and rapidly heating to 250 deg.C at 15 deg.C/min
(3) Conditions of Mass Spectrometry
Electron impact ion source (EI), energy 70 eV; transmission line temperature: 250 ℃; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; multiple reactions were monitored for negative ion mode (MRM) with solvent delay of 2 min.
The result shows that DB-5MSUI and DB-17MS chromatographic columns are difficult to separate ethylene oxide and target objects such as methanol, normal propyl alcohol and butylene oxide, the separation degree of the target objects is not enough, and the methanol, the ethylene oxide and the like are easy to overlap with substances such as ethanol, water and the like in a matrix to influence the detection resolution; the INNOWAX column and DB-624UI chromatographic column have good separation effect. DB-624UI column was selected as the analytical column.
Example 3 Mass Spectrometry Condition optimization
One-by-one a standard solution of 10 oxygen-containing sterilizing components was subjected to a first-order mass spectral scan in EI full scan mode at the same ionization energy of 70 eV. The optimized parameters of 10 alcohol and epoxy disinfection components are shown in a table 3, and a multi-reaction monitoring total ion current chromatogram is shown in a table 2.
The results show that both straight-chain alcohols and epoxy compounds are easy to form molecular ion peak [ M ]]+E.g. C3H8O]+(M ═ 60.1) and [ C4H10O]+(M ═ 74.1), or [ C2H4O]+(M ═ 44.1) and [ C4H8O]+(M ═ 72.1). Respectively carrying out product ion mode scanning on the molecular ions by using collision energy of 0-60 eV, and showing that the low molecular weight alcohols and the epoxy compounds are easy to form [ CHO [ ]]+(M ═ 29) molecular ion Peak, alcohol easily lost-H2O to form [ M-18]+Molecular ions of (e.g. [ C ]3H8O]+(M＝60.1)→[C3H6]+(M ═ 42.1) and [ C4H10O]+(M＝74.2)→[C4H8]+(M ═ 56.1) ion pairs; epoxy compounds are prone to loss of-CH3To form [ M-15 ]]+Molecular ions of (e.g. [ C ]2H4O]+(M＝44.1)→[CHO]+(M ═ 29.1) and [ C3H6O]+(M＝58.1)→[C2H3O]+(M ═ 43.0) ion pairs.
TABLE 310 quantitative and qualitative ion-pair and collision energy numbers for optimized alcohol and epoxy disinfecting ingredients
Example 4 methodological validation
1. Linear Range and quantitative lower bound of the method
Accurately weighing 6 parts of a blank sample of the no-clean hand sanitizer 1.0g, weighing a certain weight of a representative sample (10 alcohol and epoxy disinfection components, compounds in table 4) for each part of the blank sample of the no-clean hand sanitizer, putting the blank sample of the no-clean hand sanitizer and the representative sample together into a 50mL volumetric flask filled with distilled water in advance, and carrying out constant volume by using distilled water to obtain 6 parts of diluent, wherein each part of diluent contains 10 alcohol and epoxy compounds with the same concentration, and finally, the diluent with the concentrations of 1.0, 2.0, 5.0, 10.0, 20.0 and 50.0ng/mL of the 10 alcohol and epoxy compounds is formed. And (3) filling 40mL of the diluent into a purge bottle, adding 20 mu L of 10 mu g/mL diethyl ether standard stock solution below the solution surface, sealing by an upper screw cap, and automatically injecting by placing a purge and capture injector. The conditions for purging trap-gas chromatography/tandem mass spectrometry were the optimized conditions described previously. Standard working solutions were prepared with matrix-carrying dilutions. And (5) blowing, trapping and injecting samples, and drawing a standard working curve. The 10 alcohols and epoxy compounds have good linearity in the concentration range of 1.0-50.0ng/mL, and the correlation coefficient is 0.9951-0.9998. The method has the quantitative limit of 0.10-0.23ng/mL by taking the 10-fold signal-to-noise ratio (S/N) as the lowest quantitative limit, which is equivalent to the content of 0.005-0.0115 mug/g in the sample. The linear equation, correlation coefficient and quantitative lower limit of 10 alcohols and epoxy compounds are shown in Table 4.
TABLE 4 Linear regression equation and correlation coefficient
2. Accuracy and precision of the method
Selecting a sample of the commercial no-clean hand sanitizer, weighing 1.0g of the hand sanitizer, dissolving the hand sanitizer in 50mL of distilled water, transferring 40mL of the hand sanitizer, placing the hand sanitizer in a screw cap blowing bottle, and sequentially adding an epoxy compound standard solution and an internal standard solution into the hand sanitizer to prepare standard solutions with the concentrations of 1.0, 5.0 and 20.0 ng/mL. 40mL of the prepared standard solution with the concentration of 1.0, 5.0 and 20.0ng/mL is taken to be put into a screw-cap bottle, sample injection is carried out through blowing and trapping, and gas chromatography mass spectrometry is carried out, wherein each condition is the optimized condition of the previous embodiment. The standard recovery of 3 concentration levels with matrix samples is tested, parallel samples are prepared, each addition level is tested for 6 times in parallel, and the calculation precision is shown by the result: the recovery rate of the alcohols and the epoxy compounds ranges from 85.1 percent to 116.0 percent, and the relative standard deviation RSD is less than or equal to 5.3 percent. The recovery and relative standard deviation are shown in table 5.
TABLE 5 recovery and relative standard deviation of alcohol and epoxy disinfecting ingredients
EXAMPLE 5 testing of actual samples
The method is characterized in that the oxygen-containing alcohol and epoxy compound in more than 2000 batches of imported and exported disinfection liquid soap (including hand washing gel, foam liquid soap, disinfection spray, no-clean liquid soap and the like) samples for spot check are determined by adopting the optimized back method, and each sample is tested for 2 times in parallel. The test result shows that methanol in more than 20 import and export spot check samples exceeds the standard, other samples containing isopropanol, propanol, isobutanol, ethylene oxide, a small amount of propylene oxide and the like are detected, the concentration of the methanol is respectively 12.4 mu g/g-65.7 mu g/g, the concentration of the isopropanol is respectively 21.7 mu g/g-63.1 mu g/g, the concentration of the propanol is respectively 14.9 mu g/g-24.8 mu g/g, and the concentration of the ethylene oxide is respectively 5.4 mu g/g-0.5 mu g/g. In the screening, 3 samples directly replace ethanol by methanol, and the content of methanol is up to 51.7%. Other samples all meet the limit requirements of 'disinfectant raw material list and forbidden substances' GB 38850-. Wherein, fig. 3 is a data statistical chart of the test results of 16 representative samples in the import/export disinfection hand sanitizer, and 1 or more oxygen-containing disinfection components are detected in the 16 samples except for sample 3 and sample 6; the highest isopropanol detection rate was followed by methanol and isobutanol, as well as ethylene oxide and propylene oxide. FIG. 4a is a multi-reaction monitoring chromatogram of a sample of one of the leave-in hand sanitizers at the import and export locations, indicating that methanol, isopropanol, n-propanol, isobutanol, and butanol are detected in the sample of the leave-in hand sanitizer. FIG. 4b is a multi-reaction monitoring chromatogram of another sample of a leave-on hand sanitizer in an import-export sanitizing hand sanitizer, indicating that methanol was detected from the sample of the leave-on hand sanitizer.
In conclusion, the invention adopts the purging and trapping-gas chromatography-tandem mass spectrometry technology to establish the method for measuring the alcohol and epoxy disinfection components in the disinfection hand sanitizer: diluting a sample with distilled water, blowing, trapping and injecting the sample, and measuring by adopting a gas chromatography-tandem mass spectrometry multiple reaction monitoring mode. The detection method can effectively reduce the interference of ethanol, water and the like which are substrates in a conventional method to detection, has universality on disinfection liquid soap products, is simple and convenient, has high sensitivity and good precision and accuracy, can meet the batch detection requirement of alcohols and epoxy disinfection components in import and export disinfection liquid soap products, and provides technical support for market monitoring of oxygen-containing disinfection liquid soap.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for detecting oxygen-containing disinfection components in a disinfection hand sanitizer is characterized by comprising the following steps:
s1: diluting the disinfection hand sanitizer by using water as a solvent to obtain a sample to be tested;
s2: taking an internal standard substance as a reference, performing analysis and determination by utilizing a purging trapping-gas chromatography/tandem mass spectrometry method and adopting a multi-reaction monitoring mode, and determining the content of the oxygen-containing disinfection component in the sample to be detected;
wherein, the conditions of purging and trapping in S2 are as follows: the blowing temperature is 40-50 ℃; the purging time is 5-10 min; the desorption temperature is 225-300 ℃, and the desorption time is 3-5 min;
the stationary phase of chromatographic column selected by gas chromatography is bonded/cross-linked polyethanol or dimethyl siloxane.
2. The detection method according to claim 1, wherein the oxygen-containing disinfection component is one or more of an alcohol compound or an epoxy compound.
3. The detection method according to claim 2, wherein the alcohol compound is one or more of methanol, isopropanol, n-propanol, isobutanol, or n-butanol.
4. The detection method according to claim 2, wherein the epoxy compound is one or more of 2, 3-butylene oxide, 2-vinyl ethylene oxide, epichlorohydrin, ethylene oxide and propylene oxide.
5. The detection method according to claim 1, wherein the dilution in S1 is 25 to 50 times.
6. The detection method according to claim 1, wherein the conditions for purging and trapping in S2 are as follows: purging with high-purity helium gas at a flow rate of 40 mL/min; the temperature of the dry purging is 20 ℃, the time of the dry purging is 1min, and the flow rate of the dry purging is 100 mL/min.
7. The method of claim 1, wherein the column is an INNOWAX column or a DB-624UI column.
8. The detection method according to claim 1, wherein the column flow rate of the chromatographic column in S2 is 1.0mL/min, the sample injection temperature is 240-250 ℃, and the split ratio is 10: 1; and heating to 50 ℃ at a heating rate of 5 ℃/min by taking 30-35 ℃ as an initial temperature, and then heating to 250 ℃ at a heating rate of 15 ℃/min.
9. The detection method according to claim 1, wherein the mass spectrum conditions in S2 are: electron bombardment of the ion source (EI) with an energy of 70eV, negative ion mode (MRM) with multiple reaction monitoring, solvent delay of 2 min.
10. The detection method according to claim 1, wherein the internal standard substance is diethyl ether.
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