Rapid detection method for migration quantity of chloropropanol compounds in cigarette paper

Abstract

The invention belongs to the technical field of material analysis, and provides a method for rapidly detecting the migration quantity of chloropropanol compounds in cigarette paper, which comprises the following steps: carrying out a water phase migration experiment on a cigarette paper sample to be detected to obtain a migration liquid; adding deuterated chloropropanol into the migration liquid, mixing with an internal standard stock solution, and carrying out salting-out auxiliary liquid-liquid extraction, dehydration purification and nitrogen blowing concentration to obtain a liquid to be detected; a gas chromatography-tandem mass spectrometry method is adopted to measure the to-be-measured liquid, a chromatographic column is an ultra-high inert bonded polyethylene glycol capillary chromatographic column, and data are collected in a multi-reaction monitoring mode; the migration amount of the chloropropanol compounds in the sample is calculated through an internal standard method, and the chloropropanol compounds comprise 1, 3-dichloro-2-propanol and 3-chloro-1, 2-propylene glycol. The method does not need a derivatization step, is high in detection accuracy, and can realize rapid detection and batch analysis.

Description

Technical Field

[0001] This application relates to the field of materials analysis technology, and in particular to a rapid detection method for the migration of chloropropanol compounds in cigarette paper. Background Technology

[0002] 1,3-Dichloro-2-propanol (1,3-DCP) and 3-chloro-1,2-propanediol (3-MCPD), two chloropropanol compounds, mainly originate from the hydrolysis products of wet-strength agents (such as polyamide-epoxychloropropane resin) and other additives widely used in the papermaking process. With increasingly stringent regulations on chloropropanol compounds, GB 4806.8-2022, the National Food Safety Standard for Food Contact Paper and Paperboard Materials and Products, clearly stipulates that 1,3-DCP must not be detected in the aqueous extracts of food contact paper and paperboard materials and products, and the residual amount of 3-MCPD must not exceed 12 μg / L.

[0003] Currently, most of the methods for detecting chloropropanol in relevant standards employ gas chromatography / mass spectrometry (GC-MS). However, due to the limited sensitivity of direct GC-MS detection of chloropropanol, heptafluorobutyryl imidazole derivatization is required to improve detection sensitivity. However, the derivatization process is time-consuming, cumbersome, and requires advanced operational skills, limiting throughput and hindering batch sample processing, thus increasing the difficulty for laboratories at all levels to conduct this detection.

[0004] With the development of science and technology, various more advanced methods for detecting chloropropanol have emerged, but they still cannot effectively solve the aforementioned problems. For example, patent application CN114295742A discloses a method for testing the migration of chloropropanol and fatty acid esters in packaging materials. The steps include preparation of chloropropanol standard working solution, preparation of deuterated chloropropanol standard working solution, migration, purification, derivatization, gas chromatography-mass spectrometry analysis, qualitative confirmation, and quantitative analysis. This method still includes a derivatization step, and uses an HP-5MS column and SIM scanning for mass spectrometry. Although this method has lower hardware costs, when faced with complex and variable tobacco paper matrices and the requirement for detecting extremely low concentrations of migration, its analysis time is long, separation ability is insufficient, anti-interference ability is weak, and sensitivity is low, easily leading to inaccurate quantitative results, poor repeatability, and even false positives.

[0005] For example, patent application CN118688332A discloses a method for detecting 1,3-dichloro-2-propanol and 3-chloro-1,2-propanediol. The method involves first extracting sample fragments with ethyl acetate and concentrating the extract; then using acetic anhydride as a derivatizing reagent and concentrated sulfuric acid as a catalyst to derivatize the extract, obtaining a derivatized solution; the derivatized solution undergoes liquid-liquid extraction, and the organic phase is filtered through a membrane to obtain the test solution; the test solution is then analyzed by gas chromatography-tandem mass spectrometry. Although this method uses a CD-WAX column and multiple reaction monitoring (MRM) for mass spectrometry, it still introduces complex, unstable, and interference-prone derivatization reactions, resulting in a lengthy procedure, high operational risk, low analytical efficiency, and potential new accuracy issues. The extract from cigarette paper has a complex composition, potentially containing compounds with other functional groups such as alcohols, aldehydes, and acids. Under strong acid catalysis, these substances may also undergo derivatization reactions with acetic anhydride, producing more and more complex byproducts, increasing the complexity of the chromatogram, and even when using MRM mode, they may bring unpredictable matrix effects in chromatographic separation or ion source.

[0006] For example, patent application CN120522328A discloses a sample pretreatment method and GC-MS method for the simultaneous detection of glycidol and monochloropropanol in heated cigarette aerosol. The sample pretreatment method for the simultaneous detection of glycidol and monochloropropanol in heated cigarette aerosol includes the following steps: collecting particulate matter in the heated cigarette aerosol; mixing the collected material with ethyl acetate and an internal standard for extraction to obtain an extract, which is then diluted with n-hexane; adding heptafluorobutyryl imidazole for derivatization; and washing and drying the solution after derivatization to obtain the test solution. Although this method simplifies the sample pretreatment steps, its reliance on derivatization and the use of the SIM detection mode, which has weak anti-interference capabilities, result in significant drawbacks in terms of analysis speed, operational safety, method robustness, anti-interference capability, and long-term operating costs. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a rapid detection method for the migration of chloropropanol compounds in cigarette paper. This method eliminates the need for derivatization steps, is simple to operate, fast and efficient, exhibits high sensitivity, accuracy, and precision, and has a wide linear range. It can meet the needs for rapid detection and batch analysis of the migration of two chloropropanol compounds in cigarette paper, providing reliable technical support for the safety supervision of cigarette paper.

[0008] To achieve the above and related objectives, this invention provides a rapid detection method for the migration of chloropropanol compounds in cigarette paper, comprising the following steps:

[0009] (1) The paper sample to be tested was subjected to an aqueous phase migration experiment to obtain the migration liquid;

[0010] (2) Add deuterated chloropropanol mixed internal standard stock solution to the migration solution, and obtain the test solution by salting-out assisted liquid-liquid extraction, dehydration purification and nitrogen blowing concentration;

[0011] (3) The test solution was determined by gas chromatography-tandem mass spectrometry, wherein the chromatographic column was an ultra-inert bonded polyethylene glycol capillary column, and the data was collected by multiple reaction monitoring mode.

[0012] (4) The migration amount of chloropropanol compounds in the sample is calculated by internal standard method, wherein chloropropanol compounds include 1,3-dichloro-2-propanol and 3-chloro-1,2-propanediol.

[0013] Further, in step (2), the deuterated chloropropanol mixed internal standard stock solution is an ethyl acetate solution containing 1,3-dichloro-2-propanol-D5 and 3-chloro-1,2-propanediol-D5, wherein the concentration of each internal standard component is 1000 mg / L.

[0014] Further, in step (2), the liquid-liquid extraction satisfies at least one of the following conditions (a) to (b):

[0015] (a) Extraction was performed using ethyl acetate solution, which was a migration solution containing deuterated chloropropanol internal standard working solution and sodium chloride.

[0016] (b) The volume ratio of ethyl acetate solution to migration fluid is 3:5.

[0017] Furthermore, in step (3), the column length is 30m, the inner diameter is 0.25mm, and the film thickness is 0.25μm.

[0018] Further, in step (3), the gas chromatography conditions include: injection port temperature 250℃; the temperature program is: initial temperature 50℃ held for 1 min, temperature increased to 140℃ at 20℃ / min, and then temperature increased to 250℃ at 10℃ / min held for 5 min; the carrier gas is helium, constant flow mode, flow rate 1.0 mL / min; the injection volume is 1 μL, splitless injection.

[0019] Furthermore, in step (3), the mass spectrometry conditions include: electron bombardment ion source, ionization energy 70 eV; transfer line temperature 250℃, ion source temperature 280℃; the measurement mode is multiple reaction monitoring mode, and the solvent delay is 3 min.

[0020] Furthermore, the parameters for the multiple reaction monitoring mode include: 1,3-DCP quantitative ion pair 79.0 / 43.1, collision energy 5 eV, qualitative ion pair 81.0 / 43.1, collision energy 10 eV; 3-MCPD quantitative ion pair 79.0 / 43.1, collision energy 5 eV, qualitative ion pair 61.0 / 43.1, collision energy 5 eV; 1,3-DCP-D5 quantitative ion pair 82.0 / 46.1, collision energy 5 eV, qualitative ion pair 84.0 / 46.1, collision energy 10 eV; 3-MCPD-D5 quantitative ion pair 64.0 / 46.1, collision energy 5 eV, qualitative ion pair 82.0 / 46.1, collision energy 5 eV.

[0021] Further, in step (1), the aqueous phase migration experiment includes: adding an aqueous solution to the sample, placing it at 23℃±2℃ for 24h, and shaking it intermittently to obtain the migration liquid.

[0022] Furthermore, in step (1), the ratio of the sample to the aqueous solution is 10g:200mL.

[0023] Furthermore, the method also includes a blank experiment, in which steps (2) to (3) are repeated without a sample to obtain a blank value for correction.

[0024] The beneficial technical effects of this invention are as follows:

[0025] This invention optimizes the pretreatment process of traditional detection methods by using ethyl acetate liquid-liquid extraction instead of traditional diatomaceous earth solid-phase extraction. This avoids the impact of packing compaction on detection repeatability during solid-phase extraction and eliminates the need for derivatization steps, greatly simplifying the operation process, shortening the detection time, and increasing the detection throughput, making it suitable for batch sample processing.

[0026] This invention utilizes a deuterated chloropropanol mixed internal standard stock solution to offset recovery rate differences caused by the pretreatment process, ensuring the accuracy and precision of the final detection results. Furthermore, due to the complex composition of the migration liquid in cigarette paper, the matrix in the ion source can suppress or enhance the ionization efficiency of the target analyte, leading to a suppressed or elevated detection signal and producing artifacts. This invention utilizes a deuterated chloropropanol mixed internal standard stock solution to ensure stable and reliable quantitative results even when dealing with cigarette paper samples from different sources and batches. Secondly, this invention utilizes simultaneous injection and analysis of the internal standard and the target analyte, which can effectively correct for instrument response drift, ensuring the long-term stability and reproducibility of the detection method.

[0027] This invention selects ethyl acetate as the extraction solvent, which has good extraction efficiency for 1,3-DCP and 3-MCPD, and is immiscible with water and has low toxicity. Combined with the optimized volume ratio of ethyl acetate solution to migration liquid of 3:5, it can ensure the full extraction of the target analytes while reducing the amount of solvent used.

[0028] This invention employs gas chromatography / tandem mass spectrometry (GC / MS) combined with multiple reaction monitoring (MRM) mode, significantly improving the selectivity and sensitivity of detection while effectively reducing matrix interference. Optimized GC column and temperature program ensure good separation of the two target analytes and their internal standard, with symmetrical peak shapes and no obvious tailing. Furthermore, this invention exhibits a wide linear range and good linearity (R0). 2 The limit of detection (LOD) was >0.999, the limit of quantitation (LOQ) was 2.0 μg / L, and the limit of quantitation (LOQ) was 6.0 μg / L, which met the limit requirements of GB4806.8-2022. The spiked recovery rate was between 99.5% and 100.6%, and the relative standard deviation (RSD) was less than 6.3%, which showed high accuracy and precision.

[0029] This invention reduces the instrument analysis time to 28 minutes, enabling rapid analysis and detection. It is applicable to the detection of 1,3-DCP and 3-MCPD migration in various types of cigarette paper, including tipping paper, forming paper, and inner lining paper, providing reliable technical support for the safety supervision of cigarette paper and helping to control safety risks associated with cigarette paper.

[0030] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application. Attached Figure Description

[0031] The accompanying drawings, incorporated in and forming part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application. It is obvious that the drawings described below are merely some embodiments of this application, and those skilled in the art can obtain other drawings based on these drawings without inventive effort. In the drawings:

[0032] Figure 1 This is the total ion chromatogram of the standard solution in Example 1 of this application;

[0033] Figure 2 This is the total ion flow chromatogram of the actual sample in Example 1 of this application;

[0034] Figure 3 This is a schematic diagram illustrating the extraction effect of Example 1 and Comparative Examples 2 to 5 of this application;

[0035] Figure 4This is a schematic diagram showing the peak shape retention of 3-MCPD under long-term injection in Example 1 and Comparative Examples 7 and 8 of this application. Detailed Implementation

[0036] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should be understood that certain features of the invention (described in the context of separate embodiments for clarity) may also be provided in a single embodiment. Conversely, multiple features of the invention (described in the context of a single embodiment for brevity) may also be provided separately or in any suitable combination or, where appropriate, in any other described embodiment of the invention. Certain features described in the context of various embodiments will not be considered essential features of those embodiments unless the embodiment is inoperable without those elements. The invention is further illustrated below by specific examples; however, it should be noted that the specific process conditions and results described in the embodiments of the invention are merely illustrative and should not be construed as limiting the scope of protection of the invention. All equivalent changes or modifications made in accordance with the spirit and essence of the invention should be covered within the scope of protection of the invention.

[0037] First, it should be noted that all reagents used in this application are of analytical grade, and the water is Grade I water as specified in GB / T6682; ethyl acetate (C4H8O2): chromatographic grade;

[0038] 1,3-Dichloro-2-propanol standard (C3H6Cl2O, CAS: 96-23-1, English abbreviation: 1,3-DCP): purity ≥98%, or standard substance with national certification and authorized standard substance certificate.

[0039] 3-Chloro-1,2-propanediol Standard (C3H7ClO2, CAS: 96-24-2, English abbreviation: 3-MCPD): Purity ≥98%, or a standard substance certified by the state and authorized with a standard substance certificate.

[0040] 1,3-Dichloro-2-propanol-D5 standard (C3H6Cl2OD5, CAS: 1173020-20-6, English abbreviation: 1,3-DCP-D5): purity ≥98%, or a standard substance certified by the state and authorized with a standard substance certificate.

[0041] 3-Chloro-1,2-Propanediol-D5 Standard (C3H7ClO2D5, CAS: 342611-01-2, English abbreviation: 3-MCPD-D5): Purity ≥98%, or a standard substance certified by the state and authorized with a standard substance certificate.

[0042] This application provides a rapid detection method for the migration of chloropropanol compounds in cigarette paper, comprising the following steps:

[0043] (1) The paper sample to be tested was subjected to an aqueous phase migration experiment to obtain the migration liquid.

[0044] Furthermore, this step is detailed as follows:

[0045] (1.1) Sampling shall be conducted in accordance with the provisions of YC / T 207-2014, and the cigarette paper shall be cut into pieces no larger than 1cm. 2 After thoroughly mixing the fragments, weigh 10g (accurate to 0.1mg) and place it in a 50mL Erlenmeyer flask with a stopper.

[0046] (1.2) Add an aqueous solution to the sample and place it at 23℃±2℃ for 24 h with intermittent shaking to allow 1,3-DCP and 3-MCPD in the sample to migrate fully into the water to obtain a migration solution. The ratio of the sample to the aqueous solution is 10 g: 200 mL.

[0047] (2) Add deuterated chloropropanol mixed internal standard stock solution to the migration solution, and obtain the test solution by salting-out assisted liquid-liquid extraction, dehydration purification and nitrogen blowing concentration.

[0048] Furthermore, the deuterated chloropropanol mixed internal standard stock solution in this step is an ethyl acetate solution containing 1,3-dichloro-2-propanol-D5 and 3-chloro-1,2-propanediol-D5, wherein the concentration of each internal standard component is 1000 mg / L, and its preparation process is as follows:

[0049] Accurately weigh 10 mg each of 1,3-DCP-D5 and 3-MCPD-D5 standards (accurate to 0.01 mg), dissolve in ethyl acetate, transfer to a 10 mL volumetric flask, and dilute to the mark with ethyl acetate. Store in a refrigerator at 0℃~4℃ protected from light. Shelf life is 6 months.

[0050] Furthermore, the specific steps of this application are as follows:

[0051] (2.1) Accurately transfer 10 mL of the supernatant of the above migration solution into a clean test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution (1,3-DCP-D5 and 3-MCPD-D5 concentrations are both 1000 mg / L), then add 2 g of sodium chloride, and vortex mix until the sodium chloride is completely dissolved to improve the partition coefficient of chloropropanol in the organic phase.

[0052] (2.2) Extract the extract using ethyl acetate solution. The extract is a migration solution containing deuterated chloropropanol internal standard working solution and sodium chloride. The volume ratio of ethyl acetate solution to migration solution is 3:5. For example, add 6 mL of ethyl acetate as the extraction solvent, vortex mix for 5 min to fully transfer chloropropanol into the organic phase; then place the test tube in a benchtop centrifuge to separate the layers, and transfer the upper organic phase to a 10 mL glass test tube.

[0053] (2.3) Add 2g of anhydrous sodium sulfate to a glass test tube containing the organic phase, let it stand for 10min to remove water, take 4mL of supernatant and transfer it to a nitrogen blow-off tube, concentrate it to 1mL under a nitrogen concentrator at 45℃ water bath to obtain the test solution.

[0054] (3) The test solution was determined by gas chromatography-tandem mass spectrometry, with an ultra-inert bonded polyethylene glycol capillary column and data acquisition using multiple reaction monitoring mode.

[0055] Furthermore, in this step, the chromatographic column has a length of 30 m, an inner diameter of 0.25 mm, and a film thickness of 0.25 μm. The gas chromatography conditions include: an injection port temperature of 250 °C; a temperature program of initial temperature 50 °C held for 1 min, increasing to 140 °C at 20 °C / min, and then increasing to 250 °C at 10 °C / min held for 5 min; helium as the carrier gas, constant flow mode, flow rate 1.0 mL / min; and an injection volume of 1 μL, splitless injection.

[0056] Furthermore, in this step, the mass spectrometry conditions include: electron impact ion source, ionization energy 70 eV; transfer line temperature 250 °C, ion source temperature 280 °C; measurement mode is multiple reaction monitoring mode, solvent delay 3 min.

[0057] Furthermore, the parameters for the multiple reaction monitoring mode in this step are shown in Table 1 below:

[0058] Table 1

[0059]

[0060] Furthermore, this method also includes: a blank experiment, in which the sample is not added, steps (2) to (3) are repeated to perform gas chromatography-tandem mass spectrometry analysis to obtain a blank value for correction, thereby eliminating interference from reagents, instruments and experimental environment.

[0061] (4) The migration amount of chloropropanol compounds in the sample is calculated by internal standard method, wherein chloropropanol compounds include 1,3-dichloro-2-propanol and 3-chloro-1,2-propanediol.

[0062] Furthermore, this step is detailed as follows:

[0063] (4.1) Plotting the standard working curve: First, prepare the deuterated chloropropanol internal standard working solution. The preparation process is as follows:

[0064] Deuterated chloropropanol mixed stock solution (1000 mg / L): Weigh 10 mg each of 1,3-dichloro-2-propanol standard and 3-chloro-1,2-propanediol standard (accurate to 0.1 mg), dissolve in ethyl acetate in a 10 mL volumetric flask, and dilute to volume to prepare a stock solution with a concentration of 1000 mg / L; store in a refrigerator at 0℃~4℃ protected from light, shelf life 6 months;

[0065] Deuterated chloropropanol mixed standard intermediate solution 1 (10 mg / L): Accurately transfer 0.1 mL of deuterated chloropropanol mixed stock solution into a 10 mL volumetric flask, dilute to the mark with ethyl acetate to prepare an intermediate solution with a concentration of 10 mg / L. Store in a refrigerator at 0℃~4℃ protected from light. Shelf life is 3 months.

[0066] Deuterated chloropropanol mixed standard intermediate solution 2 (1 mg / L): Accurately transfer 1 mL of deuterated chloropropanol mixed standard intermediate solution 1 into a 10 mL volumetric flask, dilute to the mark with ethyl acetate to prepare an intermediate solution with a concentration of 1 mg / L, and store in a refrigerator at 0℃~4℃ protected from light. Shelf life is 3 months.

[0067] Deuterated chloropropanol internal standard working solution: Take five 50mL test tubes, add 10.00mL of water to each tube, and accurately add 0.04mL and 0.10mL of deuterated chloropropanol mixed standard intermediate solution 2 and 0.02mL, 0.05mL, 0.10mL, and 0.20mL of deuterated chloropropanol mixed standard intermediate solution 1 to each tube, respectively, to obtain deuterated chloropropanol internal standard working solutions with concentrations of 4.0μg / L, 10.0μg / L, 20.0μg / L, 50.0μg / L, 100.0μg / L, and 200.0μg / L. The deuterated chloropropanol internal standard working solution must be prepared fresh before use.

[0068] After pretreatment as described in step (2), the samples were analyzed by GC-MS / MS (gas chromatography-tandem mass spectrometry). A standard working curve was plotted with the ratio of the peak area of ​​the quantitative ion of the analyte (1,3-DCP, 3-MCPD) to the peak area of ​​the quantitative ion of the internal standard (corresponding D5 label) in each deuterated chloropropanol internal standard working solution as the ordinate and the analyte concentration as the abscissa. The linear equation was obtained, and the linear correlation coefficient R was required. 2 >0.995.

[0069] (4.2) Calculate the migration amount: Based on the ratio of the quantitative ion peak area of ​​1,3-DCP and 3-MCPD in the test solution to the quantitative ion peak area of ​​the internal standard, substitute it into the linear equation of the standard working curve to calculate the concentration of the two compounds in the test solution, and then calculate the migration amount of 1,3-DCP and 3-MCPD in the cigarette paper.

[0070] The present invention will be described in detail below through specific examples and embodiments. It should also be understood that the following embodiments are only for specific illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0071] Example 1

[0072] (1) Sampling shall be carried out in accordance with the provisions of YC / T 207-2014, and the samples shall be cut into pieces no larger than 1 cm. 2 The fragments were mixed and weighed to an accuracy of 0.1 mg. The fragments were placed in a 50 mL Erlenmeyer flask with a stopper, 200 mL of water was added, the flask was capped, and the mixture was placed at 23℃±2℃ for 24 h with occasional shaking to obtain the migration fluid.

[0073] (2) Accurately transfer 10 mL of the supernatant of the migration solution into a test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution, then add 2 g of sodium chloride. After complete dissolution, add 6 mL of ethyl acetate solution and vortex for 5 min. Centrifuge to separate the layers, transfer the upper organic phase to a 10 mL glass test tube, add 2 g of anhydrous sodium sulfate, let stand for 10 min, take 4 mL of the supernatant into a nitrogen blow-off tube, concentrate it to 1 mL in a 45℃ water bath with nitrogen, and obtain the test solution.

[0074] (3) Without adding samples, repeat the above steps and perform GC-MS / MS analysis.

[0075] (4) The test solution was determined by gas chromatography-tandem mass spectrometry. The chromatographic column was an ultra-inert bonded polyethylene glycol capillary column with a length of 30 m, an inner diameter of 0.25 mm, and a film thickness of 0.25 μm. The gas chromatography conditions included: injection port temperature of 250 °C; temperature program of initial temperature of 50 °C held for 1 min, increasing to 140 °C at 20 °C / min, and then increasing to 250 °C at 10 °C / min held for 5 min; carrier gas was helium, constant flow mode, flow rate of 1.0 mL / min; injection volume of 1 μL, splitless injection.

[0076] Mass spectrometry conditions included: electron impact ion source, ionization energy 70 eV; transfer line temperature 250 °C, ion source temperature 280 °C; measurement mode was multiple reaction monitoring (MRM), solvent delay 3 min. The parameters for multiple reaction monitoring (MRM) modes include: 1,3-DCP: quantitative ion pair 79.0 / 43.1, collision energy 5 eV; qualitative ion pair 81.0 / 43.1, collision energy 10 eV; 3-MCPD: quantitative ion pair 79.0 / 43.1, collision energy 5 eV; qualitative ion pair 61.0 / 43.1, collision energy 5 eV; 1,3-DCP-D5: quantitative ion pair 82.0 / 46.1, collision energy 5 eV; qualitative ion pair 84.0 / 46.1, collision energy 10 eV; 3-MCPD-D5: quantitative ion pair 64.0 / 46.1, collision energy 5 eV; qualitative ion pair 82.0 / 46.1, collision energy 5 eV.

[0077] (5) Perform GC-MS / MS analysis on the deuterated chloropropanol internal standard working solution. The vertical axis represents the ratio of the peak area of ​​the quantitative ion of the analyte to the peak area of ​​the quantitative ion of the internal standard, and the horizontal axis represents the concentration of the analyte. Plot a standard working curve. The linear correlation coefficient R of the working curve is calculated. 2 >0.995. A standard curve should be prepared for each experiment. After every 20 sample measurements, a standard solution of medium concentration should be added. If the measured value differs from the original value by more than 5%, the standard curve should be prepared again.

[0078] Comparative Example 1

[0079] The difference between this comparative example and Example 1 is as follows:

[0080] (2) Cut the composite membrane bag sample to be tested into fragments with a side length of less than 0.5 cm and mix them well; weigh 1.00 g (accurate to 0.0001 g) of sample into a 25 mL colorimetric tube, add 0.04 mL of deuterated chloropropanol mixed internal standard stock solution, add 12 mL of ethyl acetate, and extract by sonication for 180 min. After cooling to room temperature, transfer the extract completely to a nitrogen blowing tube, wash the residue with 3 mL of ethyl acetate, and combine the solutions in a nitrogen blowing tube. Concentrate the extract to about 0.5 mL by nitrogen blowing at 35 °C, and then transfer it to a 20 mL headspace vial (the concentrated solution should not contain visible water droplets).

[0081] Add 0.11 mL of acetic anhydride and 10 μL of concentrated sulfuric acid to a headspace vial, seal the vial, vortex to mix, and incubate at 60 °C for 60 min in an oven. Remove and cool to room temperature, then open the vial and add 1.0 mL of n-hexane, 2.0 mL of water, and approximately 0.5 g of sodium chloride. Vortex for 0.5 min. Allow to separate into layers, and take approximately 1 mL of the upper layer solution and filter it through an organic filter membrane into a small vial to obtain the test solution.

[0082] Comparative Example 2

[0083] The difference between this comparative example and Example 1 is as follows:

[0084] (2) Accurately transfer 10 mL of the supernatant of the migration solution into a test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution, then add 2 g of sodium chloride. After complete dissolution, add 5 mL of ethyl acetate solution and vortex for 5 min. Centrifuge to separate the layers, transfer the upper organic phase to a 10 mL glass test tube, add 2 g of anhydrous sodium sulfate, let stand for 10 min, take 4 mL of the supernatant into a nitrogen blow-off tube, and concentrate it to 1 mL in a 45℃ water bath by nitrogen blowing to obtain the test solution.

[0085] Comparative Example 3

[0086] The difference between this comparative example and Example 1 is as follows:

[0087] (2) Accurately transfer 10 mL of the supernatant of the migration solution into a test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution, then add 2 g of sodium chloride. After complete dissolution, add 8 mL of ethyl acetate solution and vortex for 5 min. Centrifuge to separate the layers, transfer the upper organic phase to a 10 mL glass test tube, add 2 g of anhydrous sodium sulfate, let stand for 10 min, take 4 mL of the supernatant into a nitrogen blow-off tube, and concentrate it to 1 mL by nitrogen blowing in a 45℃ water bath to obtain the test solution.

[0088] Comparative Example 4

[0089] The difference between this comparative example and Example 1 is as follows:

[0090] (2) Accurately transfer 10 mL of the supernatant of the migration solution into a test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution, then add 2 g of sodium chloride. After complete dissolution, add 10 mL of ethyl acetate solution and vortex for 5 min. Centrifuge to separate the layers, transfer the upper organic phase to a 10 mL glass test tube, add 2 g of anhydrous sodium sulfate, let stand for 10 min, take 4 mL of the supernatant into a nitrogen blow-off tube, and concentrate it to 1 mL in a 45℃ water bath by nitrogen blowing to obtain the test solution.

[0091] Comparative Example 5

[0092] The difference between this comparative example and Example 1 is as follows:

[0093] (2) Accurately transfer 10 mL of the supernatant of the migration solution into a test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution, then add 2 g of sodium chloride. After complete dissolution, add 12 mL of ethyl acetate solution and vortex for 5 min. Centrifuge to separate the layers, transfer the upper organic phase to a 10 mL glass test tube, add 2 g of anhydrous sodium sulfate, let stand for 10 min, take 4 mL of the supernatant into a nitrogen blow-off tube, and concentrate it to 1 mL in a 45℃ water bath by nitrogen blowing to obtain the test solution.

[0094] Comparative Example 6

[0095] The difference between this comparative example and Example 1 is as follows:

[0096] (2) Accurately transfer 10 mL of the supernatant of the migration solution into a test tube, accurately add 0.10 mL of deuterated chloropropanol mixed internal standard stock solution, mix and add to the diatomaceous earth solid phase extraction column, let stand for 10 min, rinse with 20 mL of n-hexane, discard the eluent, elute with 30 mL of ethyl acetate, collect the eluent, concentrate to dryness by nitrogen blowing, dissolve the residue with 2 mL of n-hexane and transfer to a 10 mL stoppered glass tube, add 5 mL of anhydrous sodium sulfate and mix well, dehydrate to form a purified solution, let stand for 10 min, take 4 mL of the supernatant into a nitrogen blowing tube, concentrate to 1 mL by nitrogen blowing in a 45℃ water bath to obtain the test solution.

[0097] Comparative Example 7

[0098] The difference between this comparative example and Example 1 is as follows:

[0099] (4) The chromatographic column is WAX (polyethylene glycol stationary phase column).

[0100] Comparative Example 8

[0101] The difference between this comparative example and Example 1 is as follows:

[0102] (4) The chromatographic column is INNOWAX (high polarity cross-linked polyethylene glycol column).

[0103] Comparative Example 9

[0104] The difference between this comparative example and Example 1 is as follows:

[0105] (4) The chromatographic column was HP-5MS (5% phenyl-95% dimethyl polysiloxane).

[0106] Comparative Example 10

[0107] The difference between this comparative example and Example 1 is as follows:

[0108] (4) The mass spectrometry conditions are SIM scan.

[0109] Performance testing

[0110] Methodological evaluation: Using actual samples of tipped paper, recovery and precision experiments were conducted on the examples and comparative examples using a spiking method at 3 concentration levels. Each spiking level was measured 5 times. The final methodological evaluation results are shown in Tables 2 and 3. The total ion chromatogram of the standard solution in Example 1 is shown below. Figure 1 As shown, the total ion chromatogram of the actual sample in Example 1 is as follows. Figure 2 As shown.

[0111] Analysis time: The overall analysis and instrumental analysis time of the examples and comparative examples were measured, and the results are shown in Figure 4.

[0112] Extraction effect: The extraction effect of Examples 2 to 5 and Comparative Examples 2 to 5 was tested, and the results are as follows: Figure 3 As shown.

[0113] Peak shape retention of 3-MCPD under long-term injection: The peak shape retention of 3-MCPD under long-term injection was detected in Examples 7 and 8, and the results are as follows. Figure 4 As shown.

[0114] The experimental data and analysis are as follows:

[0115] Table 2

[0116]

[0117] Table 3

[0118]

[0119] Continued from Table 3

[0120]

[0121] Continued from Table 3

[0122]

[0123] Table 4

[0124]

[0125] As shown in Tables 2 to 4, the evaluation results of the detection method in Example 1 of this application are superior to those of the comparative examples. Figure 1 and Figure 2 This application has a wide linear range and a good linear relationship (R). 2The limit of detection (LOD) is >0.999%, the limit of quantitation (LOQ) is 2.0 μg / L, and the limit of detection (LOQ) is 6.0 μg / L, which meets the limit requirements of GB 4806.8-2022. The spiked recovery rate is between 99.5% and 100.6%, and the relative standard deviation (RSD) is less than 6.3%, indicating high accuracy and precision. Furthermore, the instrument analysis time and overall analysis time of the detection method in this application embodiment are both shorter than the analysis time of each comparative example, enabling rapid and efficient detection.

[0126] Comparative Example 1 introduces a derivatization step. The efficiency of the derivatization reaction is affected by concentration and matrix, making it difficult to ensure complete and stable derivation at all concentration points. This may lead to disproportionate responses at high concentration points, thus affecting linearity. Therefore, the linear range of Comparative Example 1 becomes narrower and the linear relationship deteriorates. In addition, the lengthy steps increase the loss of target analytes, resulting in a significant increase in the limits of detection and quantitation. The internal standard correction effect is poor, and the long pretreatment time leads to a sharp increase in the overall analysis.

[0127] In Comparative Example 2, incomplete extraction led to a decrease in recovery rate, and the internal standard method was not fully corrected. As a result, the limit of detection and limit of quantitation increased, and the detection accuracy and precision decreased.

[0128] The amount of ethyl acetate solution used for extraction in Comparative Examples 3 to 5 increased, such as Figure 3 As shown, the extraction effects of Comparative Examples 2 to 5 were not as good as those of Example 1, and the extraction efficiency of Comparative Examples 3 to 5 decreased, the signal was weaker, and the noise effect increased, resulting in higher limits of detection and quantitation, and decreased detection accuracy and precision. However, Comparative Examples 2 to 5 used the same gas chromatography-tandem mass spectrometry analysis as this application, and the instrument analysis time was basically the same. This mainly affects the accuracy of detection.

[0129] Comparative Example 6 uses solid-phase extraction, which is cumbersome, has high losses, low and unstable recovery rates, thus increasing the detection limit and quantitation limit, decreasing detection accuracy and precision, and increasing analysis time.

[0130] Comparative Examples 7 and 8 used polyethylene glycol chromatographic columns different from those used in this application, combined with Figure 4 The columns of Comparative Examples 7 and 8 lacked sufficient inertness, resulting in peak tailing, poor reproducibility, and a certain degree of impact on instrument analysis time. Furthermore, the WAX ​​and INNOWAX columns had short lifespans, and after a certain amount of sample injection, the broadening and tailing of 3-MCPD gradually became severe, making them unsuitable for long-term analysis of chloropropanol compounds. However, after using the column of Example 1 of this application, the peak shape of 3-MCPD was improved, with symmetrical peaks and no obvious tailing.

[0131] Comparative Example 9 used an HP-5MS column, where the target analyte and matrix co-eluted, making accurate quantification and integration impossible, and all data were invalid.

[0132] Comparative Example 10 used SIM scanning, which had no impact on instrument analysis time. However, SIM relies solely on retention time and the mass number of one (or a few) precursor ions for qualitative analysis, resulting in weak evidence. In complex matrices, these peaks alone cannot confirm that the detected compound is the target compound, leading to a high risk of false positives. Therefore, Comparative Example 10 exhibited higher limits of detection and quantitation, but decreased detection accuracy and precision.

[0133] Therefore, through the combined effects of optimized pretreatment process and optimized chromatographic column and mass spectrometry conditions, this application can omit the derivatization step, and has the advantages of simple operation, high speed and efficiency, high detection sensitivity, good accuracy, excellent precision and wide linear range. It can meet the needs of rapid detection and batch analysis of the migration of two chloropropanol compounds in cigarette paper, and provide reliable technical support for the safety supervision of cigarette paper.

[0134] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A rapid detection method for the migration of chloropropanol compounds in cigarette paper, characterized in that, Includes the following steps: (1) The paper sample to be tested was subjected to an aqueous phase migration experiment to obtain the migration liquid; (2) Add deuterated chloropropanol mixed internal standard stock solution to the migration solution, and obtain the test solution by salting-out assisted liquid-liquid extraction, dehydration purification and nitrogen blowing concentration; (3) The test solution was determined by gas chromatography-tandem mass spectrometry, wherein the chromatographic column was an ultra-inert bonded polyethylene glycol capillary column, and the data was collected by multiple reaction monitoring mode. (4) Calculate the migration amount of chloropropanol compounds in the sample using the internal standard method, wherein the chloropropanol compounds include 1,3-dichloro-2-propanol and 3-chloro-1,2-propanediol.

2. The rapid detection method according to claim 1, characterized in that, In step (2), the deuterated chloropropanol mixed internal standard stock solution is an ethyl acetate solution containing 1,3-dichloro-2-propanol-D5 and 3-chloro-1,2-propanediol-D5, wherein the concentration of each internal standard component is 1000 mg / L.

3. The rapid detection method according to claim 2, characterized in that, In step (2), the liquid-liquid extraction satisfies at least one of the following conditions (a) to (b): (a) Extraction is performed using ethyl acetate solution, wherein the extract is the migration solution containing the deuterated chloropropanol internal standard working solution and sodium chloride; (b) The volume ratio of the ethyl acetate solution to the migration liquid is 3:

5.

4. The rapid detection method according to claim 1, characterized in that, In step (3), the chromatographic column has a length of 30m, an inner diameter of 0.25mm, and a film thickness of 0.25μm.

5. The rapid detection method according to claim 4, characterized in that, In step (3), the gas chromatography conditions include: injection port temperature 250℃; the temperature program is: initial temperature 50℃ held for 1 min, temperature increased to 140℃ at 20℃ / min, and then temperature increased to 250℃ at 10℃ / min held for 5 min; the carrier gas is helium, constant flow mode, flow rate 1.0 mL / min; the injection volume is 1 μL, splitless injection.

6. The rapid detection method according to claim 1, characterized in that, In step (3), the mass spectrometry conditions include: electron bombardment ion source, ionization energy 70 eV; transfer line temperature 250℃, ion source temperature 280℃; measurement mode is multiple reaction monitoring mode, solvent delay 3 min.

7. The rapid detection method according to claim 6, characterized in that, The parameters of the multiple reaction monitoring mode include: 1,3-DCP quantitative ion pair 79.0 / 43.1, collision energy 5 eV, qualitative ion pair 81.0 / 43.1, collision energy 10 eV; 3-MCPD quantitative ion pair 79.0 / 43.1, collision energy 5 eV, qualitative ion pair 61.0 / 43.1, collision energy 5 eV; 1,3-DCP-D5 quantitative ion pair 82.0 / 46.1, collision energy 5 eV, qualitative ion pair 84.0 / 46.1, collision energy 10 eV; 3-MCPD-D5 quantitative ion pair 64.0 / 46.1, collision energy 5 eV, qualitative ion pair 82.0 / 46.1, collision energy 5 eV.

8. The rapid detection method according to claim 1, characterized in that, In step (1), the aqueous phase migration experiment includes: adding an aqueous solution to the sample, placing it at 23℃±2℃ for 24h, and shaking it intermittently to obtain the migration liquid.

9. The rapid detection method according to claim 8, characterized in that, In step (1), the ratio of the sample to the aqueous solution is 10g:200mL.

10. The rapid detection method according to claim 1, characterized in that, The method also includes a blank experiment, in which steps (2) to (3) are repeated without the sample to obtain a blank value for correction.

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