CN103630624A - Method for determining 18 phthalic acid ester compounds in cigarette paper materials - Google Patents
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- CN103630624A CN103630624A CN201310600773.9A CN201310600773A CN103630624A CN 103630624 A CN103630624 A CN 103630624A CN 201310600773 A CN201310600773 A CN 201310600773A CN 103630624 A CN103630624 A CN 103630624A
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Abstract
The invention discloses a method for determining 18 phthalic acid ester compounds in cigarette paper materials. The method comprises the steps of pretreating a cigarette paper material sample to prepare a sample solution, preparing a standard solution of 18 phthalic acid ester compounds, detecting and analyzing the sample solution and standard solution respectively by adopting liquid chromatography-tandem mass spectrum, and then quantitatively analyzing by adopting an external standard method to calculate the content of 18 phthalic acid ester compounds in the cigarette paper materials. The method has the advantages of being simple and fast to operate, simple for sample pretreatment, higher in sensitivity, high in detection speed, lower in detection limit, better in reproducibility, higher in recovery rate, stronger in anti-inference capability, more accurate in qualitativeness and the like. The determination method can cope with stricter cigarette security requirement, thus providing standardized guidance for the use of PAEs (phthalic acid esters) plasticizer in cigarette industry.
Description
Technical field
The present invention relates to the assay method of phthalate compound, refer to particularly the assay method of 18 kinds of phthalate compounds in paper material for a kind of cigarette.
Background technology
Plasticiser has another name called plastifier, is the flexible macromolecular material auxiliary agent of enhancing of industrial use, and phthalate compound (PAEs) has been widely used in the processing and manufacturing of wrappage as plastifier.In recent years, the illegal interpolation of plasticiser in food and cause the relevant report of environmental pollution of common occurrence.PAEs shows accumulation, and long term exposure may cause breeding unsoundness in PAEs, even has the harm of teratogenesis, carcinogenic, mutagenesis and physiology toxicity.
The detection method of PAEs mainly contains liquid phase chromatography (LC), vapor-phase chromatography (GC), GC-MS(gas chromatography-mass spectrography) (GC/MS), Liquid Chromatography-Mass Spectrometry (LC/MS), gas chromatography-tandem mass spectrometry (GC-MS/MS), Liquid Chromatography-tandem Mass method (LC-MS/MS) etc.
In production of cigarettes process, in the adhesive glue using in the processing of ink material and composite print wrapping paper, all may have that PAEs's is residual.Cigarette paper material is the part that cigarette directly contacts oral cavity, and the detection that it is carried out to PAEs is very important.Feng Wenning etc. utilize isopropyl alcohol-cyclohexane for the auxiliary material of solvent supersonic extraction cigarette, and GC/MS method is measured the content of 7 kinds of PAEs and 4 kinds of hexane diacid ester plasticizers simultaneously; The method of the employing isopropyl alcohol extraction-gas chromatographies such as Liu Zechun is measured 14 kinds of PAEs in cigarette tipping paper and wrapping paper; Tang Gangling etc. extract with normal hexane after utilizing water and ethanol to extract cigarette tipping paper, internal lining paper and wrapping paper, by GC/MS method, have measured 18 kinds of PAEs in extract simultaneously.
And at present, have no and use LC-MS/MS method to detect the report of PAEs in paper material for cigarette.
Summary of the invention
Object of the present invention will overcome the existing deficiency of prior art exactly, and the assay method of a kind of cigarette with 18 kinds of phthalate compounds in paper material is provided.
The assay method of 18 kinds of phthalate compounds in paper material for cigarette provided by the present invention, cigarette is prepared to sample solution with paper material sample through pre-treatment, prepare the standard solution of 18 kinds of phthalate compounds simultaneously, adopt again liquid chromatography-tandem mass spectrometry respectively described sample solution and standard solution to be detected to analysis, then with external standard method, carry out quantitative test, calculate the content of 18 kinds of phthalate compounds in smoke paper using material; Wherein, the testing conditions of liquid chromatography-tandem mass spectrometry:
Adopt C
18chromatographic column, length is 100mm, and internal diameter is 2.1mm, and packing material size is 1.8 μ m, and column temperature is 40 ℃;
Adopt gradient elution, mobile phase A is the acetic acid aqueous solution containing 5mmol/L ammonium acetate, acetic acid and water volume ratio 1:1000, and Mobile phase B is methyl alcohol, flow velocity 0.4mL/min, sample size 5 μ L, gradient elution program is as follows, and wherein following ratio is volume ratio:
During 0min, mobile phase A: Mobile phase B=30:70;
During 1.0min, mobile phase A: Mobile phase B=30:70;
During 6.0min, mobile phase A: Mobile phase B=5:95;
During 9.0min, mobile phase A: Mobile phase B=5:95;
During 9.1min, mobile phase A: Mobile phase B=30:70;
During 10.0min, mobile phase A: Mobile phase B=30:70;
Ionization mode is electro-spray ionization positive ion mode ESI
+; Electron spray voltage: 5500V; Collision atmospheric pressure: 69kPa; Gas curtain atmospheric pressure: 172kPa; Atomization gas pressure: 414kPa; Heat air pressure: 345kPa; Ion source temperature: 450 ℃; Monitoring mode: multiple-reaction monitoring MRM.
In the present invention, the preparation of described sample solution, is after cigarette is shredded with paper material, first add water infiltration, then add isopropyl alcohol or ethanol, ultrasonic extraction 10～50min, the volume ratio of described water and isopropyl alcohol or ethanol is 1:1～2, and standing rear mistake 0.22 μ m organic phase filter membrane, obtains.
In the present invention, described standard solution preparation, take 18 kinds of phthalate compound standard items, by the aqueous solution of isopropyl alcohol or ethanol, dissolve, the volume ratio of described water and isopropyl alcohol or ethanol is 1:1～2, by stepwise dilution, preparation standard items concentration is respectively the series list mark of 1ng/ml, 5ng/ml, 10ng/ml, 20ng/ml, 50ng/ml, 100ng/ml, 200ng/ml and 500ng/ml or/and mixed mark solution.
In the present invention, described 18 kinds of phthalate compounds are repefral (DMP), diethyl phthalate (DEP), diallyl phthalate (DAP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), phthalic acid two (2-methoxy ethyl) ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxyethyl group) ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxyethyl group) ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethylhexyl) ester (DEHP), diphenyl phthalate, di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP).
Beneficial effect of the present invention is: LC-MS/MS condition of the present invention makes 18 kinds of phthalate compounds in 9min, obtain fine separation, and standard working curve has good linear relationship.Assay method fast and reliable of the present invention, the range of linearity is 1～500ng/mL, and qualitative detecting is limited to 0.01～1.85mg/kg (S/N=3), and the recovery is between 82.8%～111.6%, and relative standard deviation (RSD) is less than 10%.
Compare with existing detection method, LC-MS/MS method of the present invention, has that simple and quick, sample pre-treatments is simple, sensitivity is higher, detection speed is fast, detection limit is lower, reappearance is better, the recovery is higher, antijamming capability is stronger and the qualitative advantage such as more accurate.Assay method of the present invention can be tackled more strict tobacco safety requirements, for the use of PAEs class plastifier in tobacco business provides standardization, instructs.
Accompanying drawing explanation
Fig. 1 is the MRM figure of the standard solution of 18 kinds of PAEs.
Fig. 2 is the MRM figure of DMEP standard solution.
Fig. 3 is the MRM figure of DMP standard solution.
Fig. 4 is the MRM figure of DEEP standard solution.
Fig. 5 is the MRM figure of DEP standard solution.
Fig. 6 is the MRM figure of DAP standard solution.
Fig. 7 is the MRM figure of diphenyl phthalate standard solution.
Fig. 8 is the MRM figure of isomers DIBP and DBP standard solution.
Fig. 9 is the MRM figure of BBP standard solution.
Figure 10 is the MRM figure of DBEP standard solution.
Figure 11 is the MRM figure of DPP standard solution.
Figure 12 is the MRM figure of DCHP standard solution.
Figure 13 is the MRM figure of isomers BMPP and DHXP standard solution.
Figure 14 is the MRM figure of isomers DEHP and DNOP standard solution.
Figure 15 is the MRM figure of isomers DINP and DNP standard solution.
Figure 16 be sample when pre-treatment, the influence curve figure of extraction time to extraction efficiency.
Embodiment
In order to explain better the present invention, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but they do not form restriction to the present invention.
Material and reagent: cigarette used comprises cigarette tipping paper, internal lining paper, tobacco shred and box packaging paper with paper material; 0.22 μ m organic phase filter membrane is purchased from Town in Shanghai spectrum scientific instrument company limited.Ammonium acetate (AR is purchased from Chemical Reagent Co., Ltd., Sinopharm Group); Methyl alcohol, ethanol (CP is purchased from German CNW company).Purity >=99% of 18 kinds of PAEs standard items, is purchased from German Dr.Ehrenstorfer GmbH company.
Instrument: Agilent 1290 infinity-AB API4000 Ultra Performance Liquid Chromatographies-triple quadrupole rods tandem mass spectrometry instrument (American AB SCIEX company); AL204 electronic balance (sensibility reciprocal: 0.0001g, Switzerland METTLER TOLEDO company); Milli-Q Advantage A10 ultrapure water instrument (U.S. Millipore company); KQ-800KDE type high power numerical control ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.).
1) sample solution preparation: cigarette is carried out to cutting with paper material according to the regulation of YC171-2009, obtain long 200mm, the sample of wide 40mm.Sample is placed on balance and is weighed, be accurate to 0.1mg, and sample is cut into the fragment that is not more than 0.5cm * 0.5cm with scissors; Fragment is placed in to 100mL tool plug triangular flask, accurately adds 20mL water, infiltrate 30min; Then accurately add 20mL ethanol, ultrasonic extraction 30min, standing rear mistake 0.22 μ m organic phase filter membrane, obtains sample solution.
2) standard solution preparation: take 18 kinds of PAEs standard items, by the aqueous solution of ethanol, dissolve, the volume ratio of described water and ethanol is 1:1～2, by stepwise dilution, preparation standard items concentration is respectively series list mark and the mixed mark solution of 1ng/ml, 5ng/ml, 10ng/ml, 20ng/ml, 50ng/ml, 100ng/ml, 200ng/ml and 500ng/ml.
The testing conditions of LC-MS/MS:
Chromatographic column: Agilent ZORBAX Eclipse Plus-C
18(100mm * 2.1mmi.d., 1.8 μ m); Column temperature: 40 ℃;
Adopt gradient elution, mobile phase A is the acetic acid aqueous solution containing 5mmol/L ammonium acetate, acetic acid and water volume ratio 1:1000, Mobile phase B is methyl alcohol, flow velocity 0.4mL/min, sample size 5 μ L, the analyzing total time is 10min, and gradient elution program is as follows, and wherein following ratio is volume ratio:
During 0min, mobile phase A: Mobile phase B=30:70;
During 1.0min, mobile phase A: Mobile phase B=30:70;
During 6.0min, mobile phase A: Mobile phase B=5:95;
During 9.0min, mobile phase A: Mobile phase B=5:95;
During 9.1min, mobile phase A: Mobile phase B=30:70;
During 10.0min, mobile phase A: Mobile phase B=30:70;
Ionization mode is electro-spray ionization positive ion mode ESI
+; Electron spray voltage: 5500V; Collision atmospheric pressure: 69kPa; Gas curtain atmospheric pressure: 172kPa; Atomization gas pressure: 414kPa; Heat air pressure: 345kPa; Ion source temperature: 450 ℃; Monitoring mode: multiple-reaction monitoring MRM.
When the present invention selects at mass spectrum condition optimizing, adopt the 18 kinds of mono-mark of PAEs solution of 100ng/mL under positive ion mode, to carry out parent ion scanning, select [M+H] of every kind of material
+peak is parent ion, after finding parent ion, daughter ion is scanned, by optimization, go a bunch voltage (DP) value and collision energy (CE) value, make the abundance of quota ion maximum, the abundance of qualitative ion is taken second place, utilize the daughter ion find out and parent ion composition quota ion to qualitative ion pair.Mass spectrum acquisition parameter after 18 kinds of PAEs optimize is as shown in table 1.
Mass spectrum acquisition parameter after 18 kinds of PAEs of table 1 optimize
3) working curve and detectability
Under above-mentioned testing conditions, quantitative by external standard method, respectively standard solution is carried out to LC-MS/MS and detect analysis, resulting MRM figure is as shown in Fig. 1～15, and 18 kinds of phthalate compounds obtain fine separation in 9min.Wherein, tetra-pairs of isomerss of DIBP and DBP, BMPP and DHXP, DEHP and DNOP, DINP and DNP also obtain good separated, as shown in Fig. 8,13,14,15.
Peak area Y with object carries out linear regression analysis to its concentration X, obtains the standard working curve of each target compound.By 3 times of signal to noise ratio (S/N ratio)s (S/N) and 10 times of noises, recently determine qualitative detection limit and the quantitative detection limit of each compound.The retention time of each compound, equation of linear regression, related coefficient and detectability are as shown in table 2.
Working curve and the detectability of 18 kinds of PAEs of table 2
As can be seen from Table 2, the standard working curve of resulting each target compound has good linear relationship.Adopt LC-MS/MS method of the present invention, sensitivity is higher, detection limit is lower, and the range of linearity is 1～500ng/mL, and qualitative detecting is limited to 0.01～1.85mg/kg (S/N=3), quantitatively detects and is limited to 0.02～5.71mg/kg (S/N=3).
4) sample determination:
Again sample solution is carried out to LC-MS/MS and detect to analyze, if the be above standard range of linearity of working curve of the content of PAEs in sample solution, suitable sample introduction again after dilution.
Adopt this method to detect respectively 10 PAEs content that cigarette tipping papers trust sample keeps sample of 2011～2012 years and 2013.Result shows: in 10 samples of 2011～2012 years, have 2 to detect DEHP, content is respectively 1055 and 1327mg/kg; During keeping sample, 10 cigarette tipping papers trust samples of 2013 all do not detect any PAEs.Illustrate through the more strict additive control measure of tobacco business, the use of PAEs class plastifier in tobacco business be standard relatively.
Repeatability and recovery experiment
According to basic, normal, high 3 contents levels, adding respectively interpolation level in sample solution is the PAEs mixed standard solution of 50ng/mL, 200ng/mL and 500ng/mL3 concentration, every kind of concentration is added and is carried out 6 parallel laboratory tests, according to the relative standard deviation (RSD) of measured value after the recovery of standard addition of result computing method and mark-on, as shown in table 3.Result shows that the recovery of method is high, reproducible.
The recovery of table 3 method and repeatability (n=6)
As can be seen from Table 3, the recovery of the present invention is between 82.8%～111.6%, and relative standard deviation (RSD) is less than 10%, and the recovery is high, reproducible; When middle and high contents level, the recovery is higher, repeatability is better.
The selection of extraction solvent
Phthalate compound is lipophilic compound, utilizes the similar principle slective extraction solvent that mixes.The present invention, in the situation that other conditions are constant, contrasted and has directly added isopropyl alcohol, directly adds ethanol, first adds and add isopropyl alcohol after water infiltration again, first add the extraction efficiency that adds again 4 kinds of situations of ethanol after water infiltration.Experimental result shows, the amount that isopropyl alcohol, ethanol, water-isopropyl alcohol and 4 kinds of extraction solvents of water-ethanol extract DEHP is respectively 930mg/kg, 955mg/kg, 1279mg/kg and 1327mg/kg.
Therefore, cigarette is improved by the extraction efficiency of paper material sample P AEs after adding water infiltration, and the extraction efficiency of ethanol and isopropyl alcohol does not have notable difference.Therefore, this aqueous solution of testing preferred isopropyl alcohol or ethanol is as extraction solvent.
The selection of extraction time
In the situation that other conditions are constant, investigated the impact on extraction efficiency when ultrasonic time is respectively 10min, 20min, 30min, 40min and 50min, result is as shown in Figure 6.Along with the increase of ultrasonic time, the concentration of the DEHP being detected increases gradually, and when ultrasonic time reaches after 30min, continuing increase time extraction efficiency does not have significant change.Therefore, select the ultrasonic extraction time to be preferably 30min.
Optimize chromatography condition
Adopt respectively the aqueous solution of methanol-water, methyl alcohol-0.1% acetic acid aqueous solution, methyl alcohol-5mmol/L ammonium acetate and the acetic acid aqueous solution of methyl alcohol-5mmol/L ammonium acetate (acetic acid and water volume ratio 1:1000) as chromatogram flow phase.
Result shows, when using methanol-water as mobile phase, part PAEs chromatographic peak can bifurcated; And under the condition of gradient elution of the acetic acid aqueous solution of methyl alcohol-5mmol/L ammonium acetate (acetic acid and water volume ratio 1:1000) as mobile phase, LC-MS/MS chromatographic peak has good peak shape and degree of separation.
Claims (4)
1. the assay method of 18 kinds of phthalate compounds in paper material for a cigarette, it is characterized in that: cigarette is prepared to sample solution with paper material sample through pre-treatment, prepare the standard solution of 18 kinds of phthalate compounds simultaneously, adopt again liquid chromatography-tandem mass spectrometry respectively described sample solution and standard solution to be detected to analysis, then with external standard method, carry out quantitative test, calculate the content of 18 kinds of phthalate compounds in smoke paper using material; Wherein, the testing conditions of liquid chromatography-tandem mass spectrometry:
Adopt C
18chromatographic column, length is 100mm, and internal diameter is 2.1mm, and packing material size is 1.8 μ m, and column temperature is 40 ℃;
Adopt gradient elution, mobile phase A is the acetic acid aqueous solution containing 5mmol/L ammonium acetate, acetic acid and water volume ratio 1:1000, and Mobile phase B is methyl alcohol, flow velocity 0.4mL/min, sample size 5 μ L, gradient elution program is as follows, and wherein following ratio is volume ratio:
During 0min, mobile phase A: Mobile phase B=30:70;
During 1.0min, mobile phase A: Mobile phase B=30:70;
During 6.0min, mobile phase A: Mobile phase B=5:95;
During 9.0min, mobile phase A: Mobile phase B=5:95;
During 9.1min, mobile phase A: Mobile phase B=30:70;
During 10.0min, mobile phase A: Mobile phase B=30:70;
Ionization mode is electro-spray ionization positive ion mode ESI
+; Electron spray voltage: 5500V; Collision atmospheric pressure: 69kPa; Gas curtain atmospheric pressure: 172kPa; Atomization gas pressure: 414kPa; Heat air pressure: 345kPa; Ion source temperature: 450 ℃; Monitoring mode: multiple-reaction monitoring MRM.
2. the assay method of 18 kinds of phthalate compounds in paper material for cigarette according to claim 1, it is characterized in that: the preparation of described sample solution, after cigarette is shredded with paper material, first add water infiltration, add again isopropyl alcohol or ethanol, ultrasonic extraction 10～50min, the volume ratio of described water and isopropyl alcohol or ethanol is 1:1～2, standing rear mistake 0.22 μ m organic phase filter membrane, obtains.
3. the assay method of 18 kinds of phthalate compounds in paper material for cigarette according to claim 1, it is characterized in that: described standard solution preparation, take 18 kinds of phthalate compound standard items, by the aqueous solution of isopropyl alcohol or ethanol, dissolve, the volume ratio of described water and isopropyl alcohol or ethanol is 1:1～2, by stepwise dilution, preparation standard items concentration is respectively the series list mark of 1ng/ml, 5ng/ml, 10ng/ml, 20ng/ml, 50ng/ml, 100ng/ml, 200ng/ml and 500ng/ml or/and mixed mark solution.
4. according to the cigarette one of claim 1～3 Suo Shu, use the assay method of 18 kinds of phthalate compounds in paper material, it is characterized in that: described 18 kinds of phthalate compounds are repefral, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-methoxy ethyl) ester, phthalic acid two (4-methyl-2-amyl group) ester, phthalic acid two (2-ethoxyethyl group) ester, diamyl phthalate, dihexylphthalate, butyl benzyl phthalate, phthalic acid two (2-butoxyethyl group) ester, dicyclohexyl phthalate, phthalic acid two (2-ethylhexyl) ester, diphenyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate.
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| CN105866267A (en) * | 2016-03-29 | 2016-08-17 | 福建中烟工业有限责任公司 | Method for extracting residual solvent in packaging material, method for detecting residual solvent, kit for detecting residual solvent, and use of kit |
| CN106526016A (en) * | 2016-10-28 | 2017-03-22 | 陕西科技大学 | Ultra-high performance liquid chromatography-quadrupole electrostatic field orbital ion trap mass spectrometry screening method for plasticizer in milk and dairy products |
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| CN109212104A (en) * | 2018-11-13 | 2019-01-15 | 华熙福瑞达生物医药有限公司 | The remaining detection method of phthalic acid ester plasticiser in a kind of hyaluronic acid |
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| CN103995075A (en) * | 2014-05-08 | 2014-08-20 | 广州甘蔗糖业研究所 | High performance liquid chromatography-tandem mass spectrometry detection method of plasticizer in sugar |
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| CN108318463A (en) * | 2018-01-09 | 2018-07-24 | 上海烟草集团有限责任公司 | A kind of fluorescence spectrum rapid assay methods for phthalate substance in paper wrapper |
| CN109212104A (en) * | 2018-11-13 | 2019-01-15 | 华熙福瑞达生物医药有限公司 | The remaining detection method of phthalic acid ester plasticiser in a kind of hyaluronic acid |
| CN112903884A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院深圳先进技术研究院 | Method for simultaneously detecting phthalate compounds and metabolites thereof and application thereof |
| CN112903884B (en) * | 2019-11-19 | 2022-07-12 | 中国科学院深圳先进技术研究院 | Method for simultaneously detecting phthalate compounds and metabolites thereof and application thereof |
| CN113567532A (en) * | 2020-04-09 | 2021-10-29 | 湖南中烟工业有限责任公司 | Method for rapidly detecting phthalate ester components in cigarette paper |
| CN112710745A (en) * | 2020-12-08 | 2021-04-27 | 上海微谱化工技术服务有限公司 | Method for measuring di (2-ethylhexyl) phthalate (DEHP) and application thereof |
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