CN103969387A - Method for measuring content of piperitol in tobacco paper through headspace gas chromatography - Google Patents

Abstract

The invention discloses a method for measuring the content of piperitol in tobacco paper through headspace gas chromatography. The method comprises the following steps: (1), preparing an internal standard solution, a standard stock solution and a standard work solution; (2), carrying out sample pretreatment: after a cigarette sample is peeled out of a pipe tobacco and an acetate filter tip, a paper sample is directly weighted and placed into a 20 mL headspace bottle, the internal standard solution is added and sample feeding is performed after sealing to a gland; (3), sample measuring: an Agilent headspace gaschromatograph is adopted; (4), carrying out qualitative diagnosis and quantification: standard substance retention time and single standard sample introduction qualitative diagnosis are used for chromatograms of a blank solution, a standard solution and a paper solution; an internal standard method is adopted for quantification, the area ratio y and the concentration ratio x of piperitol and an internal standard peak are used for drawing working curves, so as to obtain corresponding retention time, linear equation, detection limit and determination limit. According to the method, headspace sample introduction is adopted, and the sample pretreatment is simple and easy for automation. The method has the advantages of simplicity, accuracy, automation, wide application range and the like.

Description

The method of the menthol content in Headspace Gas Chromatography Cigarette paper

Technical field

The present invention relates to cigarette detection field, relate in particular to the analytical approach of the menthol content in a kind of Headspace Gas Chromatography Cigarette paper.

Background technology

Mint type cigarette is very popular on world market, and some areas even account for the more than 25% of all sale cigarette.Mint type paper (wrapping paper and cigarette paper, tipping paper etc. for cigarette) is one of important method of producing mint type cigarette.Between production and storage life, menthol, due to high volatility, easily again moves balance between pipe tobacco, filter tip and paper (cigarette paper and tipping paper etc.), is even penetrated into external packing, and these have all increased sample size when menthol is analyzed and have analyzed difficulty.Cigarette paper peppermint content is monitored to mint type paper and between the storage life, not only the exploitation of mint type paper material is had to booster action, also significant to the character surveillance of box cigarette small packaging.Therefore, the analysis of menthol is in the urgent need to a kind of simple, effective, general method for high-flux analysis, to mint type paper stock up and the quality of storage, cigarette to carry out effective monitoring significant.

Headspace technique has that sample preparation is simple, easily robotization and the advantage such as solvent consumption is few, in conjunction with the efficient separating power of gas chromatography, has the potentiality of analyzing menthol in paper.So far there is no report adopts headspace gas chromatography to send out the research of measuring the menthol in Cigarette paper.

Summary of the invention

For the weak point of prior art existence, the invention provides the method for the menthol content in a kind of Headspace Gas Chromatography Cigarette paper.The method is simple, fast, accurately, robotization, be applicable to the robotization fast detecting to menthol content in the quality control of mint type paper in enormous quantities.

The method of the menthol content in Headspace Gas Chromatography Cigarette paper, comprises the following steps:

1) mark liquid, standard reserving solution, standard operation solution in preparation: accurately take phenylethyl propionate 0.5g in 500 mL volumetric flasks, dilute and obtain interior mark liquid with DMF constant volume, mark in 1mg/mL; Take menthol 1.0 g, phenylethyl propionate 0.1g in 100mL volumetric flask, dilute and obtain standard reserving solution, 10mg/mL menthol with DMF constant volume; Pipette standard inventory solution appropriate, be diluted to the standard operation solution of 0.1,0.25,0.50,1.0,2.0,5.0 mg/mL with interior mark liquid;

2) sample pre-treatments: randomly draw three guarantees from cigarette sample, transfer to room temperature at the state of not tearing capsule packing film open; Cigarette sample is longitudinally cut off, and separates after pipe tobacco and cellulose acetate filter, and outturn is directly weighed, and is accurate to 0.1mg, is placed in 20mL head space bottle, the interior mark liquid that to add 1.0mL concentration be 1mg/mL, sample introduction after gland packing;

3) sample determination, adopts Agilent headspace gas chromatography instrument, head space condition: 100 DEG C of equilibrium temperatures; 160 DEG C of sample loop temperature; 180 DEG C of transmission line temperature; Equilibration time 30 min; Pressurization equilibration time 0.5min; Sample injection time 0.2min;

GC conditions: carrier gas is helium, purity >=99.999%, post flow 3mL/min; Chromatographic column: Agilent HP-INNOWax chromatographic column, 30m × 0.25mm × 0.25 μ m; Input mode: split sampling, split ratio 30:1; Injector temperature: 250 DEG C; Temperature programme: 140 DEG C, keep 1min, be warming up to 220 DEG C with the speed of 20 DEG C/min, keep 2min; 250 DEG C of fid detector temperature, hydrogen 40mL/min; Air 450 mL/min; Make-up gas, helium 30mL/min;

4) quantitative and qualitative analysis: use standard items retention time and single mark sample introduction qualitative, the chromatogram of blank solution, standard solution, paper solution; Adopt inner mark method ration, menthol and interior target peak area ratio y and concentration ratio x drawing standard working curve, obtain corresponding retention time, linear equation, detection limit and detectability.

Above-mentioned outturn is the one in wrapping paper for cigarette, cigarette paper, tipping paper.

The present invention has adopted headspace sampling, and sample pre-treatments is simple and easy to robotization.Chromatographic resolution overall process only needs 7 min.The method is linear good, is quantitatively limited to 14.3 μ g/mL, and RSD is less than 4.1%, meets actual needs.The sample preparation of headspace sampling can directly be carried out at workshop, has reduced the volatilization loss of menthol, simultaneously relatively traditional solvent extraction, and solvent consumption is few, environmental friendliness.Adopt the overlapping equilibrium function of head-space sampler, the post case simultaneously multiple sample bottles of balance, to increase work efficiency, has been realized high flux automatic analysis.The method has simply, fast, accurately, robotization and the advantage such as applied widely.

Brief description of the drawings

Fig. 1 be empty solution of the present invention, standard solution, outturn solution chromatogram (wherein 1, menthol; 2, phenylethyl propionate).

Embodiment

Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.

The method of the menthol content in Headspace Gas Chromatography Cigarette paper, comprises the following steps:

1) mark liquid, standard reserving solution, standard operation solution in preparation: accurately take phenylethyl propionate 0.5g in 500 mL volumetric flasks, with DMF(N, dinethylformamide) constant volume dilution obtains interior mark liquid (mark in 1mg/mL).Take menthol 1.0 g, phenylethyl propionate 0.1g in 100mL volumetric flask, dilute and obtain standard reserving solution (10mg/mL menthol) with DMF constant volume.Pipette standard inventory solution appropriate, be diluted to the standard operation solution of 0.1,0.25,0.50,1.0,2.0,5.0 mg/mL with interior mark liquid.

2) sample pre-treatments: randomly draw three guarantees from cigarette sample, transfer to room temperature at the state of not tearing capsule packing film open.Cigarette sample is longitudinally cut off, and separates after pipe tobacco and cellulose acetate filter, and paper is directly weighed (being accurate to 0.1mg), is placed in 20mL head space bottle, and adding 1.0mL concentration is the interior mark liquid of 1mg/mL, sample introduction after gland packing;

3) sample determination, adopts Agilent headspace gas chromatography instrument, head space condition: 100 DEG C of equilibrium temperatures; 160 DEG C of sample loop temperature; 180 DEG C of transmission line temperature; Equilibration time 30 min; Pressurization equilibration time 0.5min; Sample injection time 0.2min; GC conditions: carrier gas is helium (purity >=99.999%), post flow 3mL/min; Chromatographic column: (30m × 0.25mm × 0.25 μ m) for Agilent HP-INNOWax chromatographic column; Input mode: split sampling, split ratio 30:1; Injector temperature: 250 DEG C; Temperature programme: 140 DEG C (1min) 220 DEG C (2min); 250 DEG C of fid detector temperature, hydrogen 40mL/min; Air 450 mL/min; Make-up gas (helium) 30mL/min.

4) quantitative and qualitative analysis: use standard items retention time and single mark sample introduction qualitative, the chromatogram of blank solution, standard solution, paper solution as shown in Figure 1; Adopt inner mark method ration, menthol and interior target peak area ratio y and concentration ratio x drawing standard working curve, corresponding retention time, linear equation, detection limit and detectability is as table 1:

Retention time, linear equation, detection limit and the quantitative limit of table 1 target analytes

5) recovery and reappearance: get the common tipping paper sample 0.1g of non-peppermint, add wherein respectively the menthol of basic, normal, high 3 concentration levels, replicate determination 6 times, calculates its recovery and relative standard deviation (RSD), as table 2 respectively;

The recovery of standard addition of table 2 actual sample and relative standard deviation thereof (n=6)

6) actual sample analysis: after buy on market 3 kinds of mint type cigarettes are processed, Cigarette paper is detected, result is as shown in table 3.

Menthol content (n=3) in the paper of 3 kinds of mint type cigarettes of table 3

7) advantage: the present invention has adopted headspace sampling, sample pre-treatments is simple and easy to robotization.Chromatographic resolution overall process only needs 7 min.The method is linear good, is quantitatively limited to 14.3 μ g/mL, and RSD is less than 4.1%, meets actual needs.The sample preparation of headspace sampling can directly be carried out at workshop, has reduced the volatilization loss of menthol, simultaneously relatively traditional solvent extraction, and solvent consumption is few, environmental friendliness.Adopt the overlapping equilibrium function of head-space sampler, the post case simultaneously multiple sample bottles of balance, to increase work efficiency, has been realized high flux automatic analysis.The method has simply, fast, accurately, robotization and the advantage such as applied widely.

Claims (2)

1. the method for the menthol content in Headspace Gas Chromatography Cigarette paper, is characterized in that the method comprises the following steps:

1) mark liquid, standard reserving solution, standard operation solution in preparation: accurately take phenylethyl propionate 0.5g in 500 mL volumetric flasks, dilute and obtain interior mark liquid with DMF constant volume, mark in 1mg/mL; Take menthol 1.0 g, phenylethyl propionate 0.1g in 100mL volumetric flask, dilute and obtain standard reserving solution, 10mg/mL menthol with DMF constant volume; Pipette standard inventory solution appropriate, be diluted to the standard operation solution of 0.1,0.25,0.50,1.0,2.0,5.0 mg/mL with interior mark liquid;

2) sample pre-treatments: randomly draw three guarantees from cigarette sample, transfer to room temperature at the state of not tearing capsule packing film open; Cigarette sample is longitudinally cut off, and separates after pipe tobacco and cellulose acetate filter, and outturn is directly weighed, and is accurate to 0.1mg, is placed in 20mL head space bottle, the interior mark liquid that to add 1.0mL concentration be 1mg/mL, sample introduction after gland packing;

3) sample determination, adopts Agilent headspace gas chromatography instrument, head space condition: 100 DEG C of equilibrium temperatures; 160 DEG C of sample loop temperature; 180 DEG C of transmission line temperature; Equilibration time 30 min; Pressurization equilibration time 0.5min; Sample injection time 0.2min;

GC conditions: carrier gas is helium, purity >=99.999%, post flow 3mL/min; Chromatographic column: Agilent HP-INNOWax chromatographic column, 30m × 0.25mm × 0.25 μ m; Input mode: split sampling, split ratio 30:1; Injector temperature: 250 DEG C; Temperature programme: 140 DEG C, keep 1min, be warming up to 220 DEG C with the speed of 20 DEG C/min, keep 2min; 250 DEG C of fid detector temperature, hydrogen 40mL/min; Air 450 mL/min; Make-up gas, helium 30mL/min;

4) quantitative and qualitative analysis: use standard items retention time and single mark sample introduction qualitative, the chromatogram of blank solution, standard solution, paper solution; Adopt inner mark method ration, menthol and interior target peak area ratio y and concentration ratio x drawing standard working curve, obtain corresponding retention time, linear equation, detection limit and detectability.

2. according to claim 1, the method for the menthol content in Headspace Gas Chromatography Cigarette paper, is characterized in that described outturn is the one in wrapping paper for cigarette, cigarette paper, tipping paper.