CN-121978243-A - 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 rapid detection method of chloropropanol compound migration in cigarette paper, which comprises the steps of carrying out an aqueous phase migration experiment on a sample of the cigarette paper to be detected to obtain migration liquid; adding deuterated chloropropanol into the migration liquid, mixing with an internal standard stock solution, performing salting-out auxiliary liquid-liquid extraction, dehydration purification and nitrogen blowing concentration to obtain a liquid to be detected, measuring the liquid to be detected by adopting a gas chromatography-tandem mass spectrometry, wherein a chromatographic column is an ultra-high inert bonding polyethylene glycol capillary chromatographic column, collecting data by adopting a multi-reaction monitoring mode, and calculating the migration amount of chloropropanol compounds in a sample by using an internal standard method, wherein the chloropropanol compounds comprise 1, 3-dichloro-2-propanol and 3-chloro-1, 2-propanediol. The invention does not need a derivatization step, has high detection accuracy and can realize rapid detection and batch analysis.

Inventors

• CHEN JIANHUA
• YANG XIN
• WANG TAO
• WANG LU
• GUO LIJUAN
• ZHAO MIN
• YE XIANGRUI
• YUE ZHIWEI
• ZHANG FENGMEI
• LIU CHUNBO
• WANG JIN
• LIU SHANSHAN
• WANG LAN
• BI YUBO
• WANG QINGHUA
• FAN ZIYAN
• ZHU RUIZHI
• FAN DUOQING
• ZHANG CHENGMING
• TANG GANGLING
• LI CHAO

Assignees

• 云南中烟工业有限责任公司

Dates

Publication Date

20260505

Application Date

20260212

Claims (10)

1. 1. A rapid detection method for migration quantity of chloropropanol compounds in cigarette paper is characterized by comprising the following steps: (1) Carrying out an aqueous phase migration experiment on a paper sample for cigarettes to be detected to obtain migration liquid; (2) Adding deuterated chloropropanol mixed internal standard stock solution into the migration solution, and obtaining solution to be detected through salting-out auxiliary liquid-liquid extraction, dehydration purification and nitrogen blowing concentration; (3) Determining the liquid to be detected by adopting a gas chromatography-tandem mass spectrometry, wherein the chromatographic column is an ultra-high inert bonding polyethylene glycol capillary chromatographic column, and acquiring data by adopting a multi-reaction monitoring mode; (4) Calculating migration amount of chloropropanol compounds in the sample by an internal standard method, wherein the chloropropanol compounds comprise 1, 3-dichloro-2-propanol and 3-chloro-1, 2-propanediol.
2. 2. The rapid detection method according to claim 1, wherein in the 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. 3. The rapid detection method according to claim 2, wherein in the step (2), the liquid-liquid extraction satisfies at least one of the following conditions (a) to (b): (a) Extracting a liquid to be extracted by using an ethyl acetate solution, wherein the liquid to be extracted is the migration liquid added with the deuterated chloropropanol internal standard working solution and sodium chloride; (b) The volume ratio of the ethyl acetate solution to the migration solution is 3:5.
4. 4. The rapid detection method according to claim 1, wherein in the step (3), the column length of the chromatographic column is 30m, the inner diameter is 0.25mm, and the film thickness is 0.25 μm.
5. 5. The rapid detection method according to claim 4, wherein in the step (3), the gas chromatography condition includes that the temperature of the sample inlet is 250 ℃, the temperature rising program is that the initial temperature is kept at 1 min, the temperature is raised to 140 ℃ at 20 ℃ per minute, the temperature is raised to 250 ℃ at 10 ℃ per minute, the temperature is kept at 5min, the carrier gas is helium, the constant flow mode is adopted, the flow rate is 1.0 mL per minute, the sample feeding amount is 1 μl, and the sample feeding is not split.
6. 6. The rapid detection method according to claim 1, wherein in the step (3), the mass spectrometry conditions comprise electron bombardment of the ion source, ionization energy of 70eV, transmission line temperature of 250 ℃ and ion source temperature of 280 ℃, and the determination mode is a multi-reaction monitoring mode, and the solvent delay is 3 min.
7. 7. The rapid detection method according to claim 6, wherein the parameters of the multi-reaction monitoring mode include 79.0/43.1 for 1,3-DCP, 5eV for collision energy, 81.0/43.1 for qualitative ion, 10eV for collision energy, 79.0/43.1 for 3-MCPD, 5eV for collision energy, 61.0/43.1 for qualitative ion, 5eV for collision energy, 82.0/46.1 for 1,3-DCP-D5, 5eV for collision energy, 84.0/46.1 for qualitative ion, 64.0/46.1 for 3-MCPD-D5, 5eV for collision energy, 82.0/46.1 for qualitative ion, and 5eV for collision energy.
8. 8. The rapid assay of claim 1 wherein in step (1), the aqueous phase migration assay comprises adding an aqueous solution to the sample, standing at 23 ℃ plus or minus 2 ℃ for 24 hours, and shaking intermittently to obtain the migration solution.
9. 9. The rapid assay method of claim 8, wherein in step (1), the ratio of sample to aqueous solution is 10g:200ml.
10. 10. The rapid detection method according to claim 1, further comprising a blank test, repeating the steps (2) to (3) without adding the sample, and performing gas chromatography-tandem mass spectrometry analysis to obtain a blank value for correction.

Description

Rapid detection method for migration quantity of chloropropanol compounds in cigarette paper Technical Field The application relates to the technical field of material analysis, in particular to a rapid detection method for migration quantity of chloropropanol compounds in cigarette paper. Background The two chloropropanol compounds of 1, 3-dichloro-2-propanol (1, 3-DCP) and 3-chloro-1, 2-propanediol (3-MCPD) are mainly derived from hydrolysis products of additives such as wet strength agents (such as polyamide-epichlorohydrin resin) widely used in the papermaking process. With the increasingly strict supervision of chloropropanol compounds, GB 4806.8-2022 (national food safety Standard food contact paper and cardboard materials and products) clearly states that 1,3-DCP cannot be detected in water extract of the food contact paper and cardboard materials and products, and the residual amount of 3-MCPD cannot exceed 12 mug/L. Currently, gas chromatography/mass spectrometry (GC-MS) is mostly adopted in the chloropropanol detection method given in the related standard, but due to the limited sensitivity of directly detecting chloropropanol by the GC-MS, the detection sensitivity is improved by the derivatization treatment of heptafluorobutyryl imidazole. However, the derivatization process is time-consuming and complicated, has high requirements on operation technology, restricts the detection flux, is unfavorable for batch sample processing, and increases the difficulty of carrying out the project detection in each stage of laboratory. With the development of scientific technology, the prior art has developed a plurality of more advanced chloropropanol detection methods, but the problems cannot be effectively solved. For example, patent application publication No. CN114295742A discloses a method for testing migration amount of chloropropanol and fatty acid ester in packaging materials, which comprises the steps of preparation of chloropropanol standard working solution, preparation of deuterated chloropropanol standard working solution, migration, purification, derivatization, gas chromatography-mass spectrometry, qualitative confirmation and quantitative analysis. The test method still comprises a derivatization step, the chromatographic column adopts HP-5MS, the mass spectrum adopts SIM scanning, and the method has lower hardware cost, but has long analysis time, insufficient separation capability, weak anti-interference capability and low sensitivity when facing to the requirements of complex and changeable paper substrates for cigarettes and extremely low-concentration migration detection, and is extremely easy to cause inaccurate quantitative results, poor repeatability and even false positives. In another example, patent application publication No. CN118688332A discloses a method for detecting 1, 3-dichloro-2-propanol and 3-chloro-1, 2-propanediol, firstly extracting fragments of a sample to be detected by ethyl acetate, concentrating an extracting solution, then using acetic anhydride as a derivatization reagent and concentrated sulfuric acid as a catalyst to derive the extracting solution to obtain a derivative solution, subjecting the derivative solution to liquid-liquid extraction, taking an organic phase filtration membrane to obtain a sample solution, and performing gas chromatography-tandem mass spectrometry detection on the sample solution. In the method, the chromatographic column adopts CD-WAX, and the mass spectrum adopts multi-reaction monitoring, but the method still introduces complicated, unstable and easily-interfered derivatization reaction, so that the method has the problems of long process, high operation risk, low analysis efficiency and possibly new accuracy. The extract of tobacco paper is complex in composition and may contain other functional group compounds such as alcohols, aldehydes, acids, etc. Under strong acid catalysis, these materials may also undergo derivatization reactions with acetic anhydride, producing more, more complex byproducts, increasing the complexity of the chromatogram, and even with MRM mode, may also bring about unpredictable matrix effects within the chromatographic separation or ion source. As another example, patent application publication No. CN120522328a discloses a sample pretreatment method and GC-MS method for simultaneously detecting glycidol and monochloropropanol in heated cigarette aerosol. The sample pretreatment method for simultaneously detecting glycidol and monochloropropanol in the heated cigarette aerosol comprises the following steps of capturing particulate matters in the heated cigarette aerosol, mixing a capturing material, ethyl acetate and an internal standard, extracting to obtain an extracting solution, diluting with normal hexane, adding heptafluorobutyryl imidazole for derivatization, washing with water after the derivatization is completed, and drying to obtain a solution to be detected. Although the method simplifies the sa