CN108303477A - A kind of heating do not burn cigarette main flume in the compounds such as alcohols detection method - Google Patents

Abstract

The present invention provide a kind of heating do not burn cigarette main flume in alcohol compound (1,2 propylene glycol, glycerine and menthol), phenols and free nicotine detection method, should detection method includes the following steps：(1) test solution is prepared；Alcohol compound in the main flume for heating the cigarette that do not burn is trapped including filter disc is used；(2) standard solution is prepared；(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn；Wherein, the GC conditions include：Chromatographic column：1301 silicagel column capillary columns of CP；The method can accurate, efficiently, environmentally friendlyly detect the content of predominant alcohols compound in cigarette mainstream flue gas (1,2 propylene glycol, glycerine and menthol) phenols and free nicotine.

Description

A kind of heating do not burn cigarette main flume in the compounds such as alcohols detection method

Technical field

The present invention relates to technical field of analytical chemistry, and in particular to it is a kind of heating do not burn cigarette main flume in 1,2- The detection method of propylene glycol, glycerine and menthol；It is a kind of heating do not burn cigarette main flume in phenolic compound inspection Survey method；It is a kind of heating do not burn cigarette main flume in free nicotine detection method.

Background technology

The tobacco product (HNB) that do not burn is heated, refers to being aspirated by heating the tobacco product that do not burn, the change in cigarette It studies a point vaporization and generates flue gas, to meet the smoking demand of people.It is only to heat due to heating the tobacco product product that do not burn (not burning) and vaporized species or the cracking for making cigarette, thus heating do not burn tobacco product main flume in harmful substance compared with It is few.Wherein, the multicomponent alcoholics compounds such as 1,2-PD, glycerine can keep the moisture of tobacco product, can reduce processing Making in the process is broken, while also having the effect for reducing irritation and improving taste, is common humectant in tobacco product；Together When, propylene glycol and glycerine can assist the ingredient in raw material to evaporate as the carrier for heating not combustion product gases；And peppermint Indispensable additive of the alcohol as mint type cigarette exists in the cigarette that do not burn largely.Therefore, it is necessary to 1,2-PD, The objects such as glycerine and menthol carry out Accurate Determining.

It has no in the prior art while measuring the report for heating propylene glycol, the content of glycerine and menthol in not combustion product gases Road.The propylene glycol in combustion product gases and the content of glycerine are not different from electronics smoke sol for heating, main flume matrix and Conventional combustion cigarette and electronics tobacco matrix have larger difference, and water content is higher；Menthol content therein also can be high In electronics smoke sol, therefore how accurately to measure simultaneously and heat propylene glycol in not combustion product gases, glycerine and menthol Content, and influence of the high moisture content to gas chromatographic analysis is eliminated, it is a problem to be solved.

Phenolic compound is the important harmful components of one kind in cigarette mainstream flue gas, and it is harmful to be put into 46 kinds of Canadian government The control ingredients list that ingredient list and WHO " tobacco product control research group " suggest, thus in Accurate Determining cigarette smoke Volatile phenol compound it is significant for cigarette Evaluation of Harmfulness.

The tobacco product (HNB) that do not burn is heated, (also known as " heating rod ") is made of a tobacco rod, length is about common The half of cigarette, by being aspirated to heating the tobacco product that do not burn, the chemical composition vaporization in cigarette generates flue gas, to Meet the smoking demand of people.Since heating does not burn tobacco product product without burning, only heating makes the substance of cigarette Vaporization or cracking, therefore heating do not burn tobacco product main flume in harmful substance it is less, simultaneously because containing in product A large amount of glycerine, main flume matrix and conventional combustion cigarette matrix have larger difference, and water content is higher.It is measuring Carry out improvement method inspection by increasing cigarette suction number merely when heating the phenolic compound in the tobacco product main flume that do not burn Substrate concentration is also improved when surveying sensitivity, can influence the separation of object.

Currently, the domestic detection in relation to phenolic compound in cigarette mainstream flue gas generally uses《YC/T 255-2008》Institute Then extraction is added using the phenolic compound in cambridge filter trapping main flume in defined high performance liquid chromatography, the method The phenolic compound on solvent supersonic extraction filter disc is taken, ultrasonic time is up to 40min, while different ultrasonic echography power are not With the repeatability for also affecting test result, therefore how accurately to measure simultaneously and heat the phenolic compound in smoke that do not burn Content, and influence of the high moisture content to gas chromatographic analysis is eliminated, it is a problem to be solved.

The strength of cigarette is related with the nicotine content in main flume, especially has more with free state nicotine therein Close relationship.But salt is formed by as weak acid and mild base salt since nicotine is combined with organic acid, is easily dissociated so that accurate to survey The absolute content for determining free state nicotine in flue gas has certain difficulty.

The tobacco product (HNB) that do not burn is heated, (also known as " heating rod ") is made of a tobacco rod, length is about common The half of cigarette, by being aspirated to heating the tobacco product that do not burn, the chemical composition vaporization in cigarette generates flue gas, to Meet the smoking demand of people.Since heating does not burn tobacco product without burning, only heating makes the vaporized species of cigarette Or cracking, therefore heating do not burn tobacco product main flume in harmful substance it is less, simultaneously because containing a large amount of in product Glycerine, main flume matrix and conventional combustion cigarette matrix have larger difference, and water content is higher.It is heated measuring Do not burn the free nicotine in tobacco product main flume when by increasing cigarette suction number, to carry out improvement method detection sensitive merely Substrate concentration is also improved when spending, and can influence the separation of object.Therefore, Accurate Determining heats the tobacco product mainstream smoke that do not burn Dissociate nicotine content in gas, does not burn the control of tobacco product sucking quality with important theory significance and practical valence to heating Value.

Currently, free nicotine in main stream cigarette smoke detection generally uses the nicotine in cambridge filter trapping main flume, Then the nicotine being added on water and chloroform extraction filter disc is extracted since Smoke Particulate is enriched on cambridge filter using water Object cannot be extracted completely when taking, and then detection data is higher using chloroform；In addition, water and chloroform liquid liquid extraction It is time-consuming longer when taking, it is up to 2-4 hours, it is inefficient, therefore how Accurate Determining heats free nicotine in not combustion product gases Content is a problem to be solved.

Invention content

For solve the problems, such as how and meanwhile measure heating not propylene glycol, the content of glycerine and menthol in combustion product gases, Present invention offer is a kind of to detect main alcohol in cigarette mainstream flue gas simultaneously using filter disc trapping, solvent extraction and through gas chromatograph The method of class compound (1,2-PD, glycerine and menthol).

The present invention heats the main phenolic compounds in main stream smoke of cigarette that do not burn for Accurate Determining, provides one kind and catches Collection solution quickly, efficiently, accurately can measure heating and not burn come the method for trapping major phenolic compound in main flume Phenolic compound in cigarette mainstream flue gas is conducive to improve the efficiency and accuracy for detecting phenolic compound.

The present invention heats the free nicotine in main stream cigarette smoke that do not burn for Accurate Determining, provides a kind of trapping solution Method to trap main free nicotine in main flume quick, efficient, accurate can measure and heat cigarette mainstream of not burning Free nicotine in flue gas is conducive to improve the efficiency and accuracy for detecting free nicotine.

The method of the invention can accurate, efficiently, environmentally friendlyly detect predominant alcohols compound in cigarette mainstream flue gas (1, 2- propylene glycol, glycerine and menthol) content.

The purpose of the present invention is adopt the following technical scheme that realize.

The present invention provide it is a kind of heating do not burn cigarette main flume in alcohol compound detection method, the detection side Method includes the following steps：

(1) test solution is prepared comprising obtained from the total granules that the main flume of cigarette is not burnt in the heating Take alcohol compound；

(2) standard solution is prepared；

(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn； Wherein, the GC conditions include：

Chromatographic column：CP-1301 silicagel column capillary columns；

Preferably, the alcohol compound is 1,2-PD, glycerine and menthol.

Preferably, in the step (1), the test solution for preparing includes：

The total granules of cigarette is trapped under ISO suction modes using filter disc, after by filter disc be put into organic solvent oscillation, mistake Filter；

Preferably, the filter disc is cambridge filter；

Preferably, the quantity of the cigarette be 3-7 branch, preferably 5；

Preferably, the organic solvent is isopropanol；

Preferably, the duration of oscillation is 20-35min, preferably 30min；

Preferably, described be filtered into is filtered using anhydrous sodium sulfate syringe filters；

Preferably, in the step (1), the test solution for preparing includes：

The total granules of 5 cigarette is collected under ISO suction modes using cambridge filter, after cambridge filter is put into In the isopropanol of 20ml in 100mL containers, 30min is vibrated at room temperature, pipettes 2mL extraction solutions, through anhydrous sodium sulfate syringe needle Filter is filtered.

Preferably, in the step (2), the standard solution for preparing includes：1,2-PD, the glycerine of 1g are taken respectively And menthol, through organic solvent constant volume；

Preferably, the organic solvent is isopropanol；

Preferably, in the step (2), the standard solution for preparing includes：

In the 1,2-PD, glycerine and menthol to 100mL containers that weigh 1g respectively, through isopropanol constant volume, shake up, Acquired solution is preserved under the conditions of 4 DEG C；Pipette respectively 0.2mL, 0.5mL, 2.5mL, 5mL, 7.5mL, 10mL, 15mL, In 20mL above-mentioned solution to 100mL containers, a concentration of 0.02mg/mL, 0.05mg/mL, 0.25mg/mL, 0.50mg/ are respectively obtained The standard solution of mL, 0.75mg/mL, 1.00mg/mL, 1.50mg/mL, 2.00mg/mL.

Preferably, the GC conditions further include：

The CP-1301 silicagel columns capillary column column length 30m, column internal diameter 0.32mm, 1 μm of film thickness；

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：50∶1；

Carrier gas：Helium, flow velocity 0.7mL/min；

Make-up gas：Helium, flow velocity 30mL/min；

Hydrogen：Flow velocity is 40mL/min；

Air：Flow velocity is 400mL/min；

Preferably, 110 DEG C of the initial temperature keep 1min, rise to 150 DEG C by 110 DEG C with 10 DEG C/min rates, keep 3min, then 220 DEG C are risen to by 150 DEG C with 30 DEG C/min rates, keep 5min.

Preferably, the detection method of alcohol compound includes following step in the main flume for heating the cigarette that do not burn Suddenly：

(1) test solution is prepared：

The total granules of 5 cigarette is collected under ISO suction modes using cambridge filter, after cambridge filter is put into In 100mL containers, the isopropanol of 20ml is added, vibrates 30min at room temperature, pipette 2mL solution, is filtered through anhydrous sodium sulfate syringe needle Device filters；

(2) standard solution is prepared：

In the 1,2-PD, glycerine and menthol to 100mL containers that weigh 1g respectively, through isopropanol constant volume, shake up, Acquired solution is preserved under the conditions of 4 DEG C；Accurately pipette respectively 0.2mL, 0.5mL, 2.5mL, 5mL, 7.5mL, 10mL, In 15mL, 20mL above-mentioned solution to 100mL containers, respectively obtain a concentration of 0.02mg/mL, 0.05mg/mL, 0.25mg/mL, The standard solution of 0.50mg/mL, 0.75mg/mL, 1.00mg/mL, 1.5.mg/mL, 2.00mg/mL；

(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn：

It takes standard solution and test solution to inject gas chromatograph to be measured, the gas chromatograph condition includes：

Chromatographic column：CP-1301 silicagel column capillary columns；Preferably, the CP-1301 silicagel columns capillary column column length 30m, Column internal diameter 0.32mm, 1 μm of film thickness；

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：50∶1；

Carrier gas：Helium, flow velocity 0.7mL/min；

Make-up gas：Helium or nitrogen, flow velocity 30mL/min；

Hydrogen：Flow velocity is 40mL/min；

Air：Flow velocity is 400mL/min；

Preferably, 110 DEG C of the initial temperature keep 1min, rise to 150 DEG C by 110 DEG C with 10 DEG C/min rates, keep 3min, then 220 DEG C are risen to by 150 DEG C with 30 DEG C/min rates, keep 5min.

Compared with prior art, the method for the detection alcohol compound content provided by the invention has below beneficial to effect Fruit：

(1) detection efficiency of the method for the invention is high, by disposably trapping predominant alcohols compound in main flume (1,2-PD, glycerine and menthol), and the contents of three kinds of alcohols in sample to be tested is detected simultaneously using gas-chromatography, it carries High working efficiency；The present invention has reached apparent effect using anhydrous sodium sulfate filter, eliminates sample higher moisture pair The influence of gas chromatographic detection；

(2) detection method of the present invention saves the consumption of a large amount of organic reagents, while cost is reduced, reduces Detect harm of the work for environment and testing staff's health；

(3) detection method of the present invention has the advantages that high sensitivity, repeatability and the rate of recovery are good.

The present invention provide it is a kind of heating do not burn cigarette main flume in phenolic compound detection method, the detection side Method includes the following steps：

(1) test solution is prepared；It includes being obtained from the total granules of the main flume for heating the cigarette that do not burn Take phenolic compound；

(2) standard solution is prepared；

(3) it uses and heats containing for alcohol compound in the main flume of the cigarette that do not burn described in high effective liquid chromatography for measuring Amount；Wherein, the high-efficient liquid phase chromatogram condition includes：

Chromatographic column：Explosive E2 columns；

Mobile phase：Acetonitrile-aqueous solution；

Preferably, the phenolic compound is o- benzenediol, p- benzenediol, phenol, o-cresol, m-cresol, p- first Phenol, m- benzenediol.

Preferably, in the step (1), the test solution for preparing includes：

The total granules of cigarette is trapped under ISO suction modes using trapping solution, after by obtained solution vibrate, mistake Filter；Wherein, the trapping solution is a concentration of 4%；

Preferably, the quantity of the cigarette be 3-7 branch, preferably 5；

Preferably, the duration of oscillation is 2-7min, preferably 5min；

Preferably, the filtering refers to using water phase membrane filtration, it is preferable to use 0.22 μm of water phase filter membrane；

Preferably, in the step (1), the test solution for preparing includes：

The total granules of 5 cigarette is trapped under ISO suction modes using trapping solution, after by obtained solution in room temperature Lower oscillation 5min, through 0.22 μm of water phase membrane filtration；

Preferably, the ratio of the quantity and trapping solution of the cigarette is 5：25ml；

Preferably, in the step (1), the test solution for preparing includes：

Total grain of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions Phase object, after by it is described two series connection trapping bottles in solution vibrate 5min at room temperature after, pipette solution 2mL obtained above, Through 0.22 μm of water phase membrane filtration.

Preferably, in the step (2), the standard solution for preparing includes：O- benzenediol, p- benzenediol are taken respectively, Phenol, organic solvent is added to being completely dissolved in o-cresol, m-cresol, p-Cresol, m- benzenediol, dilute by organic solvent It releases；

Preferably, the acetic acid aqueous solution that the organic solvent is a concentration of 4%；

Preferably, in the step (2), the standard solution for preparing includes：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, The m-cresol of 50mg, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic molten of 30mL is added Agent to after being completely dissolved, after be transferred in 100mL containers through organic solvent constant volume；

Preferably, in the step (2), the standard solution for preparing includes：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, The m-cresol of 50mg, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic molten of 30mL is added Agent to after being completely dissolved, after be transferred in 100mL containers, through organic solvent constant volume, after take the obtained solution 10mL extremely In 100mL containers, through organic solvent constant volume as primary standard solution；After take the primary standard solution 10mL to 100mL to hold In device, through organic solvent constant volume as secondary standard solution；Secondary standard solution obtained above 1,2,5mL and one are taken respectively In grade standard solution 1,2mL to 50mL containers, through organic solvent constant volume；Respectively obtain a concentration of 0.25g μ g/mL, 0.50 μ g/ The p- benzenediol standard solution of mL, 1.25 μ g/mL, 2.51 μ g/mL, 5.02 μ g/mL, 12.54 μ g/mL；A concentration of 0.07 μ g/ The m- benzenediol standard solution of mL, 0.13 μ g/mL, 0.34 μ g/mL, 0.67 μ g/mL, 1.34 μ g/mL, 3.35 μ g/mL；Concentration For the o- benzenediol standard of 0.36 μ g/mL, 0.71 μ g/mL, 1.78 μ g/mL, 3.57 μ g/mL, 7.13 μ g/mL, 17.83 μ g/mL Solution；The phenol of a concentration of 0.26 μ g/mL, 0.53 μ g/mL, 1.32 μ g/mL, 2.64 μ g/mL, 5.28 μ g/mL, 13.19 μ g/mL Standard solution；A concentration of 0.14 μ g/mL, 0.28 μ g/mL, 0.71 μ g/mL, 1.42 μ g/mL, 2.83 μ g/mL, 7.08 μ g/mL M-cresol standard solution；A concentration of 0.24 μ g/mL, 0.48 μ g/mL, 1.21 μ g/mL, 2.42 μ g/mL, 4.85 μ g/mL, 12.12 The o-cresol standard solution of μ g/mL.

Preferably, the high-efficient liquid phase chromatogram condition further includes：

The chromatographic column column internal diameter 250mm × 4.6mm,

Preferably, the grain size of the filler is 5 μm；

Preferably, the chromatographic column column temperature：20-40 DEG C, preferably 30 DEG C；

Preferably, the chromatographic column column flow is 1.0ml/min；

Preferably, the sampling volume：10μL；

Preferably, the volume ratio of the water and acetonitrile is 50: 50.

Preferably, the detection method of phenolic compound includes following step in the main flume for heating the cigarette that do not burn Suddenly：

(1) test solution is prepared：

Total grain of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions Phase object, after by it is described two series connection trapping bottles in solution vibrate 5min at room temperature after, pipette solution 2mL obtained above, Through 0.22 μm of water phase membrane filtration；

(2) standard solution is prepared：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, The m-cresol of 50mg, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic molten of 30mL is added Agent to after being completely dissolved, after be transferred in 100mL containers, through organic solvent constant volume, after take the obtained solution 10mL extremely In 100mL containers, through organic solvent constant volume as primary standard solution；After take the primary standard solution 10mL to 100mL to hold In device, through organic solvent constant volume as secondary standard solution；Secondary standard solution obtained above 1,2,5mL and one are taken respectively In grade standard solution 1,2mL to 50mL containers, through organic solvent constant volume；Respectively obtain a concentration of 0.25g μ g/mL, 0.50 μ g/ The p- benzenediol standard solution of mL, 1.25 μ g/mL, 2.51 μ g/mL, 5.02 μ g/mL, 12.54 μ g/mL；A concentration of 0.07 μ g/ The m- benzenediol standard solution of mL, 0.13 μ g/mL, 0.34 μ g/mL, 0.67 μ g/mL, 1.34 μ g/mL, 3.35 μ g/mL；Concentration For the o- benzenediol standard of 0.36 μ g/mL, 0.71 μ g/mL, 1.78 μ g/mL, 3.57 μ g/mL, 7.13 μ g/mL, 17.83 μ g/mL Solution；The phenol of a concentration of 0.26 μ g/mL, 0.53 μ g/mL, 1.32 μ g/mL, 2.64 μ g/mL, 5.28 μ g/mL, 13.19 μ g/mL Standard solution；A concentration of 0.14 μ g/mL, 0.28 μ g/mL, 0.71 μ g/mL, 1.42 μ g/mL, 2.83 μ g/mL, 7.08 μ g/mL M-cresol standard solution；A concentration of 0.24 μ g/mL, 0.48 μ g/mL, 1.21 μ g/mL, 2.42 μ g/mL, 4.85 μ g/mL, 12.12 The o-cresol standard solution of μ g/mL；

(3) it uses and heats containing for alcohol compound in the main flume of the cigarette that do not burn described in high effective liquid chromatography for measuring Amount：

It takes standard solution and test solution to inject high performance liquid chromatograph to be measured, the high performance liquid chromatograph item Part includes：

Chromatographic column：Explosive E2 columns；

Mobile phase：Acetonitrile-aqueous solution；

Preferably, the chromatographic column column internal diameter 250mm × 4.6mm,

Preferably, the grain size of the filler is 5 μm；

Preferably, the chromatographic column column temperature：20-40 DEG C, preferably 30 DEG C；

Preferably, the chromatographic column column flow is 1.0ml/min；

Preferably, the sampling volume：10μL；

Preferably, the water and acetonitrile solution volume ratio are 50: 50.

Compared with prior art, the method for detection phenols content provided by the invention has the advantages that：

(1) the method for the invention detection time is short, and the measurement main phenolic compounds in main stream smoke of cigarette period only needs Want 10 minutes or so；

(2) relative to existing method (《YC/T 255-2008》), the method for the invention saves a large amount of organic reagents Consumption reduces harm of the detection work for environment and testing staff's health while cost is reduced；

(3) present invention have the advantages that operation accurately, high sensitivity and reproducible.

The present invention provide it is a kind of heating do not burn cigarette main flume in free nicotine detection method, the detection method Include the following steps：

(1) test solution is prepared；It includes being obtained from the total granules of the main flume for heating the cigarette that do not burn Take free nicotine；

(2) standard solution is prepared；

(3) gas chromatography is used to measure the content of free nicotine in the main flume for heating the cigarette that do not burn；Its In, the GC conditions include：

Chromatographic column：CP-1301 silicagel column capillary columns；

Column volume：30m×0.32mm×1.0μm.

Preferably, in the step (1), the test solution for preparing includes：

The total granules of cigarette is trapped under ISO suction modes using trapping solution, after by obtained solution vibrate, mistake Filter；

Wherein, the trapping solution is the mixed solution of water and chloroform, and the volume ratio of the water and chloroform is 1 ∶1；

Preferably, the quantity of the cigarette be 3-7 branch, preferably 5；

Preferably, the duration of oscillation is 2-7min, preferably 5min；

Preferably, described be filtered into is filtered using anhydrous sodium sulfate syringe filters；

Preferably, in the step (1), the test solution for preparing includes：

Using trapping solution in ISO suction modes trap 5 cigarette total granules, after by obtained solution at room temperature 5min is vibrated, is filtered through anhydrous sodium sulfate syringe filters；

Preferably, the ratio of the quantity and trapping solution of the cigarette is 5：25ml；

Preferably, in the step (1), the test solution for preparing includes：

Total grain of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions Phase object, after by it is described two series connection trapping bottles in solution vibrate 5min at room temperature after, pipette solution 2mL obtained above, It is filtered through anhydrous sodium sulfate syringe filters.

Preferably, in the step (2), the standard solution for preparing includes：100mg nicotine standard product are taken, through organic molten Agent constant volume；

Preferably, the organic solvent is chloroform；

Preferably, in the step (2), the standard solution for preparing includes：

In the nicotine standard product to 50mL containers for weighing about 100mg respectively, the chloroform constant volume through 100mL；It pipettes Solution is stated to dilute through chloroform, obtain concentration be respectively 0.05mg/mL, 0.10mg/mL, 0.50mg/mL, 1.00mg/mL, The standard solution of 2.00mg/mL, 5.00mg/mL.

Preferably, the GC conditions further include：

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：20∶1；

Carrier gas：Helium, preferable flow rate 1.2mL/min；

Preferably, the make-up gas flow velocity is 10mL/min；

Preferably, the dottle pin purging flow velocity is 10mL/min；

Preferably, 100 DEG C of the initial temperature keep 0.5min, rise to 200 DEG C by 100 DEG C with 20 DEG C/min rates, protect Hold 1.5min.

Preferably, detection method includes the following steps for free nicotine in the main flume for heating the cigarette that do not burn：

(1) test solution is prepared：

Total grain of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions Phase object, after by it is described two series connection trapping bottles in solution vibrate 5min at room temperature after, pipette solution 2mL obtained above, It is filtered through anhydrous sodium sulfate syringe filters；

(2) standard solution is prepared：

In the nicotine standard product to 50mL containers for weighing about 100mg respectively, the chloroform constant volume through 100mL；It pipettes Solution is stated to dilute through chloroform, obtain concentration be respectively 0.05mg/mL, 0.10mg/mL, 0.50mg/mL, 1.00mg/mL, The standard solution of 2.00mg/mL, 5.00mg/mL；

(3) gas chromatography is used to measure the content of free nicotine in the main flume for heating the cigarette that do not burn：

It takes standard solution and test solution to inject gas chromatograph to be measured, the gas chromatograph condition includes：

Chromatographic column：CP-1301 silicagel column capillary columns；

Column volume：30m×0.32mm×1.0μm；

Preferably, injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：20∶1；

Carrier gas：Helium, flow velocity 1.2mL/min；

Preferably, the make-up gas flow velocity is 10mL/min；

Preferably, the dottle pin purging flow velocity is 10mL/min；

Preferably, 100 DEG C of the initial temperature keep 0.5min, rise to 200 DEG C by 100 DEG C with 20 DEG C/min rates, protect Hold 1.5min.

Compared with prior art, the method for detection free nicotine content provided by the invention has the advantages that：

(1) the detection method time provided by the invention is short, and the free cigarette in the main flume for the cigarette that do not burn is heated in detection The alkali period only needs 9 minutes or so；

(2) detection method provided by the invention saves the process of concussion extraction and liquid-liquid extraction after filter disc trapping, keeps away The problem of having exempted from incomplete filter method extraction, liquid-liquid extraction poor repeatability；One-step method of the present invention realizes flue gas trapping and free cigarette The process that alkali is distributed in organic phase and water phase, cigarette often aspirate the assigning process that a bite is primary free nicotine；The present invention is also The pre-treatment time of sample to be tested is saved, the sample to be tested pretreatment process of existing method needs 3-4 hours, and the present invention only needs 10min；

(3) detection method of the present invention has the advantages that operation accurate, high sensitivity and reproducible.

Description of the drawings

Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein：

Fig. 1 is detection method flow chart of the present invention；

Fig. 2 is detection alcohols method Plays solution chromatogram of the present invention；

Fig. 3 is test solution chromatogram in detection alcohols method of the present invention；

Fig. 4 is the selection to cigarette quantity in step (1) described in detection alcohols method of the present invention；

Fig. 5 is the selection to isopropanol usage amount in step (1) described in detection alcohols method of the present invention；

Fig. 6 is the selection to duration of oscillation in step (1) described in detection alcohols method of the present invention；

Fig. 7 is the method flow diagram of detection phenols of the present invention；

Fig. 8 is detection phenols method Plays solution chromatogram of the present invention；

Fig. 9 is test solution chromatogram in detection phenols method of the present invention；

Figure 10 is the series connection trapping bottle described in detection phenols method of the present invention；

Figure 11 is two trapping bottle effect cascading effects in detection phenols method of the present invention

Figure 12 is filter disc and absorption bottle cascading effect in detection phenols method of the present invention；

Figure 13 is detection free nicotine method flow diagram of the present invention；

Figure 14 is detection free nicotine method Plays solution chromatogram of the present invention；

Figure 15 is test solution chromatogram in detection free nicotine method of the present invention；

Figure 16 is the series connection trapping bottle described in detection free nicotine method of the present invention；

Figure 17 is the selection to cigarette quantity in step (1) described in detection free nicotine method of the present invention；

Figure 18 is the selection to trapping solution usage amount in step (1) described in detection free nicotine method of the present invention.

Specific implementation mode

The present invention is further described in detail With reference to embodiment, the embodiment provided is only for explaining The bright present invention, the range being not intended to be limiting of the invention.

Experimental method in following embodiments is unless otherwise specified conventional method.Medicine as used in the following examples Material raw material, reagent material etc. are commercially available products unless otherwise specified.

Reagent used in following embodiment and instrument：

Standard items：1,2-PD, glycerine, menthol, Dr.Ehrenstorfer companies, Germany；

Reagent：Isopropanol, chromatographically pure, Duksan pure chemicals companies of South Korea；

Experimental water is the deionized water of Milli-Q pure water systems；

Instrument：Gas chromatograph-fid detector, agilent company；

SM450 linear types smoking machine (Cerulean companies of Britain)；

Electronic analytical balance, sensibility reciprocal：0.0001g, Mettler companies of Switzerland；

HY-6 bilayer velocity-modulated oscillators, Guo Hua Electrical Appliances Co., Ltd；

Anhydrous sodium sulfate pin type filter, 13mm × 0.22 μm, Shanghai ANPEL Scientific Instrument Co., Ltd..

O- benzenediol, p- benzenediol, phenol, o-cresol, m-cresol, p-Cresol, m- benzenediol, German DR are public Department；

Acetonitrile solution, HPLC is pure, German CNW companies；

Acetic acid solution, HPLC is pure, Merck KGaA company；

All experimental waters are ultra-pure water instrument treated deionized water；

Instrument：SM450,20 passages type smoking machines；

High performance liquid chromatograph, agilent company；

Fluorescence detector, FLD；

AE163 electronic balances, sensibility reciprocal 0.0001g, Mettler companies of Switzerland.

Embodiment 1

(1) test solution is prepared：

The total granules of 5 cigarette is collected under ISO suction modes using cambridge filter, after cambridge filter is put into In 100mL containers, the isopropanol of 20ml is added, vibrates 30min at room temperature, pipette 2mL solution, is filtered through anhydrous sodium sulfate syringe needle Device filters；

(2) standard solution is prepared：

In the 1,2-PD, glycerine and menthol to 100mL containers that weigh about 1g respectively, it is accurate to 0.0001g, is passed through Isopropanol constant volume, shakes up, and acquired solution is preserved under the conditions of 4 DEG C；Accurately pipette respectively 0.2mL, 0.5mL, 2.5mL, In 5mL, 7.5mL, 10mL, 15mL, 20mL above-mentioned solution to 100mL containers, a concentration of 0.02mg/mL, 0.05mg/ are respectively obtained The standard solution of mL, 0.25mg/mL, 0.50mg/mL, 0.75mg/mL, 1.00mg/mL, 1.5mg/mL, 2.00mg/mL；It is shown in Table 1；

Table 1：The concentration (mg/mL) of standard solution in detection method of the present invention

(3) gas chromatograph for determination：

Chromatographic condition is as follows：

Chromatographic column：Melt silicagel column capillary column CP-1301, column length 30m, column internal diameter 0.32mm, 1 μm of film thickness；

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：50∶1；

Carrier gas：Helium, preferable flow rate 0.7mL/min；

Make-up gas：Helium or nitrogen, flow velocity 30mL/min；Hydrogen：Flow velocity is 40mL/min；Air：Flow velocity is 400mL/min；

110 DEG C of the initial temperature keeps 1min, and 150 DEG C are risen to by 110 DEG C with 10 DEG C/min rates, keeps 3min, then 220 DEG C are risen to by 150 DEG C with 30 DEG C/min rates, keeps 5min.

(4) foundation of standard curve：

Using the obtained standard solution of gas chromatograph for determination, obtain target compound (1,2-PD, glycerine and Menthol) integrated peak areas, using the integral area of target compound as ordinate, using the concentration of target compound as cross Coordinate establishes the standard curve of target compound.Using peak area quantification, with peak area (integrated value) to mass concentration (mg/ ML equation of linear regression, validation criteria curvilinear equation and related coefficient, R) are acquired²0.99 should be not less than.The standard of each compound Curve and detection limit are shown in Table 2；

Table 2：Standard curve and detection in detection method of the present invention limit

Note：The detection limit is calculated with 3 times of signal-to-noise ratio (S/N=3)

(5) methodological study of detection method of the present invention

Inventive samples are carried out with the standard solution recovery of standard addition experiment of basic, normal, high various concentration level, each sample It measures 3 times respectively, calculates predominant alcohols compound in detection method of the present invention (1,2-PD, glycerine and menthol) The rate of recovery and mark-on after measured value relative standard deviation, the results are shown in Table 3；As can be seen that in 3 mark-on levels, utilize Predominant alcohols compound (1,2-PD, glycerine and menthol) is flat in detection method detection main flume of the present invention The equal rate of recovery is 90.6-101.0%；The mean relative deviation ＜ 3.2% of sample tests；Illustrate detection side of the present invention The rate of recovery of method is higher, and repeatability is preferably.

Table 3：Recovery of standard addition investigates (n=3)

(6) sample to be tested is detected

Using the test solution of the obtained sample to be tested of gas chromatograph for determination, each compound (1,2- the third two is measured Alcohol, glycerine and menthol) chromatographic peak area, substituted into above-mentioned standard curve, respectively obtained main in sample to be tested The content of alcohol compound (1,2-PD, glycerine and menthol), is shown in Table 4；

Table 4：Heat propylene glycol, the testing result of glycerine and menthol in the cigarette mainstream flue gas that do not burn

Embodiment 2

(1) prepare test solution (with embodiment 1)；

(2) prepare standard solution (with embodiment 1)；

(3) gas chromatograph for determination (with embodiment 1)；

(4) foundation of standard curve (with embodiment 1)；

(5) methodological study of detection method of the present invention (with embodiment 1)；

(6) sample to be tested is detected

Using the test solution of the obtained sample to be tested of gas chromatograph for determination, each compound (1,2- the third two is measured Alcohol, glycerine and menthol) chromatographic peak area, substituted into above-mentioned standard curve, respectively obtained main in sample to be tested The content of alcohol compound (1,2-PD, glycerine and menthol), is shown in Table 5；

Table 5：Heat propylene glycol, the testing result of glycerine and menthol in the cigarette mainstream flue gas that do not burn

Embodiment 3

(1) prepare test solution (with embodiment 1)；

(2) prepare standard solution (with embodiment 1)；

(3) gas chromatograph for determination (with embodiment 1)；

(4) foundation of standard curve (with embodiment 1)；

(5) methodological study of detection method of the present invention (with embodiment 1)；

(6) sample to be tested is detected

Using the test solution of the obtained sample to be tested of gas chromatograph for determination, each compound (1,2- the third two is measured Alcohol, glycerine and menthol) chromatographic peak area, substituted into above-mentioned standard curve, respectively obtained main in sample to be tested The content of alcohol compound (1,2-PD, glycerine and menthol), is shown in Table 6；

Table 6：Heat propylene glycol, the testing result of glycerine and menthol in the cigarette mainstream flue gas that do not burn

Embodiment 4

(1) prepare test solution (with embodiment 1)；

(2) prepare standard solution (with embodiment 1)；

(3) gas chromatograph for determination (with embodiment 1)；

(4) foundation of standard curve (with embodiment 1)；

(5) methodological study of detection method of the present invention (with embodiment 1)；

(6) sample to be tested is detected

Using the test solution of the obtained sample to be tested of gas chromatograph for determination, each compound (1,2- the third two is measured Alcohol, glycerine and menthol) chromatographic peak area, substituted into above-mentioned standard curve, respectively obtained main in sample to be tested The content of alcohol compound (1,2-PD, glycerine and menthol), is shown in Table 7；

Table 7：Heat propylene glycol, the testing result of glycerine and menthol in the cigarette mainstream flue gas that do not burn

Embodiment 5：To the selection of cigarette quantity in detection method of the present invention

From fig. 4, it can be seen that the quantity of cigarette described in the step of detection method of the present invention (1) is 3-7 branch, preferably 5.

Embodiment 6：Selection in step (1) described in detection method of the present invention to isopropanol usage amount

From fig. 5, it can be seen that the usage amount of isopropanol described in the step of detection method of the present invention (1) is 20ml.

Embodiment 7：Selection in step (1) described in detection method of the present invention to duration of oscillation

From fig. 6, it can be seen that duration of oscillation described in the step of detection method of the present invention (1) is 20-35min, it is excellent Select 30min.

Embodiment 8

(1) test solution is prepared：

Total grain of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions Phase object, after by it is described two series connection trapping bottles in solution vibrate 5min at room temperature after, pipette solution 2mL obtained above, Through 0.22 μm of water phase membrane filtration；

Figure 11 shows two trapping bottle effect cascading effects in detection method of the present invention；Figure 12 shows the present invention Filter disc and absorption bottle cascading effect in the detection method, the results showed that, it is better than use using two trapping bottle cascading effects The effect of filter disc trapping plus absorption bottle.

(2) standard solution is prepared：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, The m-cresol of 50mg, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic molten of 30mL is added Agent to after being completely dissolved, after be transferred in 100mL containers, through organic solvent constant volume, after take the obtained solution 10mL extremely In 100mL containers, through organic solvent constant volume as primary standard solution；After take the primary standard solution 10mL to 100mL to hold In device, through organic solvent constant volume as secondary standard solution；Secondary standard solution obtained above 1,2,5mL and one are taken respectively In grade standard solution 1,2mL to 50mL containers, through organic solvent constant volume；Respectively obtain a concentration of 0.25g μ g/mL, 0.50 μ g/ The p- benzenediol standard solution of mL, 1.25 μ g/mL, 2.51 μ g/mL, 5.02 μ g/mL, 12.54 μ g/mL；A concentration of 0.07 μ g/ The m- benzenediol standard solution of mL, 0.13 μ g/mL, 0.34 μ g/mL, 0.67 μ g/mL, 1.34 μ g/mL, 3.35 μ g/mL；Concentration For the o- benzenediol standard of 0.36 μ g/mL, 0.71 μ g/mL, 1.78 μ g/mL, 3.57 μ g/mL, 7.13 μ g/mL, 17.83 μ g/mL Solution；The phenol of a concentration of 0.26 μ g/mL, 0.53 μ g/mL, 1.32 μ g/mL, 2.64 μ g/mL, 5.28 μ g/mL, 13.19 μ g/mL Standard solution；A concentration of 0.14 μ g/mL, 0.28 μ g/mL, 0.71 μ g/mL, 1.42 μ g/mL, 2.83 μ g/mL, 7.08 μ g/mL M-cresol standard solution；A concentration of 0.24 μ g/mL, 0.48 μ g/mL, 1.21 μ g/mL, 2.42 μ g/mL, 4.85 μ g/mL, 12.12 The o-cresol standard solution of μ g/mL；

(3) it uses and heats containing for phenolic compound in the main flume of the cigarette that do not burn described in high effective liquid chromatography for measuring Amount：

It takes standard solution and test solution to inject high performance liquid chromatograph to be measured, the high performance liquid chromatograph item Part includes：

Chromatographic column：Explosive E2 columns；

Mobile phase：Acetonitrile-aqueous solution；

The chromatographic column column internal diameter 250mm × 4.6mm,

The grain size of the filler is 5 μm；

The chromatographic column column temperature：20-40 DEG C, preferably 30 DEG C；

The chromatographic column column flow is 1.0ml/min；

The sampling volume：10μL；

The water and acetonitrile solution volume ratio are 50: 50.

(4) foundation of standard curve：

With o- benzenediol, p- benzenediol, phenol, o-cresol, m-cresol, p-Cresol, m- benzenediol are that detection refers to Mark prepares the standard solution of 6 kinds of phenolic compounds, through efficient liquid phase chromatographic analysis, with the chromatographic peak of phenolic compound object Area carries out regression analysis to its respective concentration, obtains standard curve and its regression equation, related coefficient, utilizes minimum concentration mark Liquid signal-to-noise ratio limits for 3 to calculate detection.As shown in Table 8, used chromatographic condition makes 6 kinds of phenols have compound chromatography Peak all detaches preferably, and all has preferable correlation, and detection limit is between 0.005 μ of μ g/cig~0.021 g/cig.

Table 8：The standard curve of the phenolic compound and detection limit

Note：Detection limit is calculated with 3 times of signal-to-noise ratio (S/N=3).

(5) calculating of phenolic compound measurement result in the cigarette mainstream flue gas that do not burn is heated

The quantitative analysis that phenolic compound is carried out with external standard method, i.e., with the chromatographic peak area of target phenolic compound to its phase It answers concentration to carry out regression analysis, obtains standard curve.Sample to be tested is measured, the color of detection target phenolic compound is measured Spectral peak area substitutes into standard curve, respectively obtains o- benzenediol, the p- benzenediol in sample to be tested, phenol, o-cresol, Between, the content of p-Cresol, m- benzenediol.

Wherein, the m-cresol and p-Cresol cannot be kept completely separate using current technology means, in chromatogram On occur with the situation of chromatographic peak, therefore both the above compound determination its summation is not measured individually.

Result of calculation, the calculation formula of phenolic compound is in cigarette mainstream flue gas：

In formula：

The transmission quantity of phenols component in every cigarette mainstream flue gas of m-, unit are microgram every (μ g/cig)；

A- extracts the concentration (μ g/mL) of phenolic compound in sample；

50- extraction solutions volume (mL)；

N- tests the number (cig) of smoking cigarette every time；

(6) methodological study of detection method of the present invention

It is horizontal that high, medium and low (2 μ g/cig, 1 μ g/cig, 0.5 μ g/cig) various concentration is carried out to sample of the present invention The experiment of standard solution recovery of standard addition, each sample measures 5 times respectively, calculates main in the various cigarette mainstream flue gas of this method The relative standard deviation of measured value, the results are shown in Table 9 after the rate of recovery and mark-on of phenolic compound；As can be seen from Table 9, at 3 In mark-on level, the average recovery rate that main phenolic compounds in main stream smoke of cigarette is detected using the method for the invention is existed Between 91.5-103.9%；The mean relative deviation of the test result is less than 3.2%, illustrates the rate of recovery of the method for the invention Higher, repeatability is preferably

Table 9：Recovery of standard addition investigates (n=5)

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of phenolic compound object, obtains standard curve； The sample to be tested prepared is measured, the chromatographic peak area of detection phenolic compound object is measured, substitutes into standard curve, Respectively obtain o- benzenediol, the p- benzenediol in sample to be tested, phenol, o-cresol, p-Cresol, m- benzenediol contain Amount, the results are shown in Table 10.

Table 10：Heat the testing result of phenolic compound in the cigarette mainstream flue gas that do not burn

Embodiment 9

(1) prepare test solution (with embodiment 8)；

(2) prepare standard solution (with embodiment 8)；

(3) high performance liquid chromatograph measures (with embodiment 8)；

(4) foundation of standard curve (with embodiment 8)；

(5) heat the calculating of phenolic compound measurement result in the cigarette mainstream flue gas that do not burn (with embodiment 8)；

(6) methodological study of detection method of the present invention (with embodiment 8)；

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of phenolic compound object, obtains standard curve； The sample to be tested prepared is measured, the chromatographic peak area of detection phenolic compound object is measured, substitutes into standard curve, Respectively obtain o- benzenediol, the p- benzenediol in sample to be tested, phenol, o-cresol, p-Cresol, m- benzenediol contain Amount, the results are shown in Table 11.

Table 11：Heat the testing result of phenolic compound in the cigarette mainstream flue gas that do not burn

Embodiment 10

(1) prepare test solution (with embodiment 8)；

(2) prepare standard solution (with embodiment 8)；

(3) gas chromatograph for determination (with embodiment 8)；

(4) foundation of standard curve (with embodiment 8)；

(5) heat the calculating of phenolic compound measurement result in the cigarette mainstream flue gas that do not burn (with embodiment 8)；

(6) methodological study of detection method of the present invention (with embodiment 8)；

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of phenolic compound object, obtains standard curve； The sample to be tested prepared is measured, the chromatographic peak area of detection phenolic compound object is measured, substitutes into standard curve, Respectively obtain o- benzenediol, the p- benzenediol in sample to be tested, phenol, o-cresol, p-Cresol, m- benzenediol contain Amount, the results are shown in Table 12.

Table 12：Heat the testing result of phenolic compound in the cigarette mainstream flue gas that do not burn

Embodiment 11

(1) prepare test solution (with embodiment 8)；

(2) prepare standard solution (with embodiment 8)；

(3) gas chromatograph for determination (with embodiment 8)；

(4) foundation of standard curve (with embodiment 8)；

(5) heat the calculating of phenolic compound measurement result in the cigarette mainstream flue gas that do not burn (with embodiment 8)；

(6) methodological study of detection method of the present invention (with embodiment 8)；

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of phenolic compound object, obtains standard curve； The sample to be tested prepared is measured, the chromatographic peak area of detection phenolic compound object is measured, substitutes into standard curve, Respectively obtain o- benzenediol, the p- benzenediol in sample to be tested, phenol, o-cresol, p-Cresol, m- benzenediol contain Amount, the results are shown in Table 13.

Table 13：Heat the testing result of phenolic compound in the cigarette mainstream flue gas that do not burn

Embodiment 12

(1) test solution is prepared：

Total grain of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions Phase object, after by it is described two series connection trapping bottles in solution vibrate 5min at room temperature after, pipette solution 2mL obtained above, It is filtered through anhydrous sodium sulfate syringe filters；

(2) standard solution is prepared：

In the nicotine standard product to 50mL containers for weighing about 100mg respectively, through chloroform constant volume；Pipette above-mentioned solution warp Chloroform dilute, obtain concentration be respectively 0.05mg/mL, 0.10mg/mL, 0.50mg/mL, 1.00mg/mL, 2.00mg/mL, 5.00mg/mL standard solution；

(3) gas chromatography is used to measure the content of free nicotine in the main flume for heating the cigarette that do not burn：

It takes standard solution and test solution to inject gas chromatograph to be measured, the gas chromatograph condition includes：

Chromatographic column：CP-1301 silicagel column capillary columns；

Column volume：30m×0.32mm×1.0μm；

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：20∶1；

Carrier gas：Helium, flow velocity 1.2mL/min；

The make-up gas flow velocity is 10mL/min；

The dottle pin purging flow velocity is 10mL/min；

100 DEG C of the initial temperature keeps 0.5min, rises to 200 DEG C by 100 DEG C with 20 DEG C/min rates, keeps 1.5min。

(4) calculating for free nicotine in main stream cigarette smoke measurement result of not burning is heated

The quantitative analysis of free nicotine is carried out with external standard method, i.e., it is corresponding dense to it with the chromatographic peak area of target free nicotine Degree carries out regression analysis, obtains standard curve.The sample to be tested prepared is measured, detection target free nicotine is measured Chromatographic peak area, substitute into standard curve, respectively obtain the free nicotine content in sample.

Result of calculation, the calculation formula for heating the free nicotine in main stream cigarette smoke that do not burn are：

In formula：

The content of every free nicotine in main stream cigarette smoke of m-, unit are microgram every (μ g/cig)；

A- extracts the concentration (μ g/mL) of free nicotine in sample；

50- extraction solutions volume (mL)；

N- tests the number (cig) of smoking cigarette every time；

(4) foundation of standard curve：

Using nicotine as Testing index, Working Standard Solution is prepared, through gas chromatographic analysis, with object chromatographic peak area pair Its respective concentration carries out regression analysis, obtains standard curve and its regression equation, related coefficient, utilizes minimum concentration standard liquid noise Detection limit is calculated when than being 3.As shown in Table 14, used chromatographic condition keeps the separation of free nicotine chromatographic peak preferable, and Preferable correlation is all had, detection is limited to 5 μ g/cig.

Table 14：Standard curve and detection in detection method of the present invention limit

Note：The detection limit is calculated with 3 times of signal-to-noise ratio (S/N=3)

(5) calculating for free nicotine in main stream cigarette smoke measurement result of not burning is heated

The quantitative analysis of free nicotine is carried out with external standard method, i.e., it is corresponding dense to it with the chromatographic peak area of target free nicotine Degree carries out regression analysis, obtains standard curve.The sample to be tested prepared is measured, detection target free nicotine is measured Chromatographic peak area, substitute into standard curve, respectively obtain the free nicotine content in sample.

Result of calculation, the calculation formula for heating the free nicotine in main stream cigarette smoke that do not burn are：

In formula：

The content of every free nicotine in main stream cigarette smoke of m-, unit are microgram every (μ g/cig)；

A- extracts the concentration (μ g/mL) of free nicotine in sample；

50- extraction solutions volume (mL)；

N- tests the number (cig) of smoking cigarette every time；

(6) methodological study of detection method of the present invention

The mark of high, medium and low (0.20mg/cig, 0.10mg/cig, 0.05mg/cig) various concentration level is carried out to sample Quasi- solution recovery of standard addition experiment, each sample measure 5 times respectively, calculate the various free nicotine in main stream cigarette smoke of this method The rate of recovery and mark-on after measured value relative standard deviation, the results are shown in Table 15.As can be seen from Table 15, in 3 mark-on water On flat, the average recovery rate of free nicotine in main stream cigarette smoke is detected between 98.3%~99.7% using the method.Sample The mean relative deviation of product test result is less than 3.1%；Illustrate that the rate of recovery of this law is higher, repeatability is preferably.

Table 15：Recovery of standard addition investigates (n=5)

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of target compound, obtains standard curve.To preparing Good sample to be tested A is measured, and measures the chromatographic peak area of detection target compound, is substituted into standard curve, is respectively obtained and wait for The content of free nicotine, the results are shown in Table 16 in sample

Table 16：Heat the testing result of free nicotine in cigarette (sample to be tested A) main flume that do not burn

Embodiment 13

(1) prepare test solution (with embodiment 12)；

(2) prepare standard solution (with embodiment 12)；

(3) high performance liquid chromatograph measures (with embodiment 12)；

(4) foundation of standard curve (with embodiment 12)；

(5) heat the calculating for free nicotine in main stream cigarette smoke measurement result of not burning (with embodiment 12)；

(6) methodological study of detection method of the present invention (with embodiment 12)；

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of target compound, obtains standard curve.To preparing The sample to be tested B that good another trade mark heats the cigarette that do not burn is measured, and measures the chromatographic peak area of detection target compound, Standard curve is substituted into, the content of free nicotine in sample to be tested is respectively obtained, the results are shown in Table 17；

Table 17：Heat the testing result of free nicotine in cigarette (sample to be tested B) main flume that do not burn

Embodiment 14

(1) prepare test solution (with embodiment 12)；

(2) prepare standard solution (with embodiment 12)；

(3) high performance liquid chromatograph measures (with embodiment 12)；

(4) foundation of standard curve (with embodiment 12)；

(5) heat the calculating for free nicotine in main stream cigarette smoke measurement result of not burning (with embodiment 12)；

(6) methodological study of detection method of the present invention (with embodiment 12)；

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of target compound, obtains standard curve.To preparing The sample to be tested C that good another trade mark heats the cigarette that do not burn is measured, and measures the chromatographic peak area of detection target compound, Standard curve is substituted into, the content of free nicotine in sample to be tested is respectively obtained, the results are shown in Table 18；

Table 18：Heat the testing result of free nicotine in cigarette (sample to be tested C) main flume that do not burn

Embodiment 15

(1) prepare test solution (with embodiment 12)；

(2) prepare standard solution (with embodiment 12)；

(3) high performance liquid chromatograph measures (with embodiment 12)；

(4) foundation of standard curve (with embodiment 12)；

(5) heat the calculating for free nicotine in main stream cigarette smoke measurement result of not burning (with embodiment 12)；

(6) methodological study of detection method of the present invention (with embodiment 12)；

(7) sample to be tested is detected

Regression analysis is carried out to its respective concentration with the chromatographic peak area of target compound, obtains standard curve.To preparing The sample to be tested D that good another trade mark heats the cigarette that do not burn is measured, and measures the chromatographic peak area of detection target compound, Standard curve is substituted into, the content of free nicotine in sample to be tested is respectively obtained, the results are shown in Table 19；

Table 19：Heat the testing result of free nicotine in cigarette (sample to be tested D) main flume that do not burn

Embodiment 16：To the selection of cigarette quantity in detection method of the present invention

As can be seen from Figure 17, in the step (1) of detection method of the present invention, the quantity of the cigarette is 3-7 Branch, preferably 5.

Embodiment 17：Selection in step (1) described in detection method of the present invention to trapping solution usage amount

As can be seen from Figure 18, the usage amount of trapping solution is in the step (1) of detection method of the present invention 25mL。

In short, specific description of embodiments of the present invention above is not intended to limit the present invention, those skilled in the art can be with It is variously modified or is deformed according to the present invention, without departing from the spirit of the present invention, right appended by the present invention should all belonged to and wanted The range asked.

Claims (15)

1. the detection method of alcohol compound in a kind of main flume heating the cigarette that do not burn, which includes following step Suddenly：

(1) test solution is prepared；It includes obtaining alcohol from the total granules of the main flume for heating the cigarette that do not burn Class compound；

(2) standard solution is prepared；

(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn；Wherein, The GC conditions include：

Chromatographic column：CP-1301 silicagel column capillary columns；

Preferably, the alcohol compound is 1,2-PD, glycerine and menthol.

2. detection method according to claim 1, which is characterized in that described to prepare test solution in the step (1) Including：

The total granules of cigarette is trapped under ISO suction modes using filter disc, after by filter disc be put into organic solvent oscillation, filtering；

Preferably, the filter disc is cambridge filter；

Preferably, the quantity of the cigarette be 3-7 branch, preferably 5；

Preferably, the organic solvent is isopropanol；

Preferably, the duration of oscillation is 20-35min, preferably 30min；

Preferably, described be filtered into is filtered using anhydrous sodium sulfate syringe filters；

Preferably, in the step (1), the test solution for preparing includes：

The total granules of 5 cigarette is collected under ISO suction modes using cambridge filter, after by cambridge filter be put into 100mL hold In the isopropanol of 20ml in device, vibrate 30min at room temperature, pipette 2mL extraction solutions, through anhydrous sodium sulfate syringe filters into Row filtering.

3. detection method according to claim 1 or 2, which is characterized in that in the step (2), the preparation standard is molten Liquid includes：The 1,2-PD, glycerine and menthol for taking 1g respectively, through organic solvent constant volume；

Preferably, the organic solvent is isopropanol；

Preferably, in the step (2), the standard solution for preparing includes：

It in the 1,2-PD, glycerine and menthol to 100mL containers that weigh 1g respectively, through isopropanol constant volume, shakes up, by institute Solution is obtained to preserve under the conditions of 4 DEG C；Accurately pipette respectively 0.2mL, 0.5mL, 2.5mL, 5mL, 7.5mL, 10mL, 15mL, In 20mL above-mentioned solution to 100mL containers, a concentration of 0.02mg/mL, 0.05mg/mL, 0.25mg/mL, 0.50mg/ are respectively obtained The standard solution of mL, 0.75mg/mL, 1.00mg/mL, 1.5.mg/mL, 2.00mg/mL.

4. detection method according to any one of claim 1 to 3, which is characterized in that the GC conditions are also wrapped It includes：

The CP-1301 silicagel columns capillary column column length 30m, column internal diameter 0.32mm, 1 μm of film thickness；

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：50:1；

Carrier gas：Helium, flow velocity 0.7mL/min；

Make-up gas：Helium or nitrogen, flow velocity 30mL/min；

Hydrogen：Flow velocity is 40mL/min；

Air：Flow velocity is 400mL/min；

Preferably, 110 DEG C of the initial temperature keep 1min, rise to 150 DEG C by 110 DEG C with 10 DEG C/min rates, keep 3min, then 220 DEG C are risen to by 150 DEG C with 30 DEG C/min rates, keep 5min.

5. detection method according to any one of claim 1 to 4, which is characterized in that described to heat the cigarette that do not burn Detection method includes the following steps for alcohol compound in main flume：

(1) test solution is prepared：

The total granules of 5 cigarette is collected under ISO suction modes using cambridge filter, after by cambridge filter be put into 100mL hold In device, the isopropanol of 20ml is added, vibrates 30min at room temperature, pipette 2mL solution, is filtered through anhydrous sodium sulfate syringe needle；

(2) standard solution is prepared：

It in the 1,2-PD, glycerine and menthol to 100mL containers that weigh 1g respectively, through isopropanol constant volume, shakes up, by institute Solution is obtained to preserve under the conditions of 4 DEG C；Accurately pipette respectively 0.2mL, 0.5mL, 2.5mL, 5mL, 7.5mL, 10mL, 15mL, In 20mL above-mentioned solution to 100mL containers, a concentration of 0.02mg/mL, 0.05mg/mL, 0.25mg/mL, 0.50mg/ are respectively obtained The standard solution of mL, 0.75mg/mL, 1.00mg/mL, 1.5.mg/mL, 2.00mg/mL；

(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn：

It takes standard solution and test solution to inject gas chromatograph to be measured, the gas chromatograph condition includes：

Chromatographic column：CP-1301 silicagel column capillary columns；Preferably, the CP-1301 silicagel columns capillary column column length 30m, in column Diameter 0.32mm, 1 μm of film thickness；

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：50:1；

Carrier gas：Helium, flow velocity 0.7mL/min；

Make-up gas：Helium or nitrogen, flow velocity 30mL/min；

Hydrogen：Flow velocity is 40mL/min；

Air：Flow velocity is 400mL/min；

Preferably, 110 DEG C of the initial temperature keep 1min, rise to 150 DEG C by 110 DEG C with 10 DEG C/min rates, keep 3min, then 220 DEG C are risen to by 150 DEG C with 30 DEG C/min rates, keep 5min.

6. the detection method of phenolic compound in a kind of main flume heating the cigarette that do not burn, which includes following step Suddenly：

(1) test solution is prepared；It includes obtaining phenol from the total granules of the main flume for heating the cigarette that do not burn Class compound；

(2) standard solution is prepared；

(3) content of alcohol compound in the main flume for heating the cigarette that do not burn described in high effective liquid chromatography for measuring is used； Wherein, the high-efficient liquid phase chromatogram condition includes：

Chromatographic column：Explosive E2 columns；

Mobile phase：Acetonitrile-aqueous solution；

Preferably, the phenolic compound be o- benzenediol, p- benzenediol, phenol, o-cresol, m-cresol, p-Cresol, M- benzenediol.

7. detection method according to claim 6, which is characterized in that described to prepare test solution in the step (1) Including：

The total granules of cigarette is trapped under ISO suction modes using trapping solution, after by obtained solution filter disc vibrate, mistake Filter；Wherein, the trapping solution is a concentration of 4%；

Preferably, the quantity of the cigarette be 3-7 branch, preferably 5；

Preferably, the duration of oscillation is 2-7min, preferably 5min；

Preferably, the filtration refers to using water phase membrane filtration, it is preferable to use 0.22 μm of water phase filter membrane；

Preferably, in the step (1), the test solution for preparing includes：

The total granules of 5 cigarette is trapped under ISO suction modes using trapping solution, after obtained solution is shaken at room temperature 5min is swung, through 0.22 μm of water phase membrane filtration；

Preferably, the ratio of the quantity and trapping solution of the cigarette is 5：25ml；

Preferably, in the step (1), the test solution for preparing includes：

The total granules of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions, After the solution in described two series connection trapping bottles is vibrated 5min at room temperature afterwards, solution 2mL obtained above is pipetted, through 0.22 μm water phase membrane filtration.

8. the detection method described according to claim 6 or 7, which is characterized in that in the step (2), the preparation standard is molten Liquid includes：O- benzenediol, p- benzenediol, phenol, o-cresol, m-cresol, p-Cresol, m- benzenediol is taken to be added respectively Organic solvent is to being completely dissolved, by organic solvent diluting；

Preferably, the acetic acid aqueous solution that the organic solvent is a concentration of 4%；

Preferably, in the step (2), the standard solution for preparing includes：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, 50mg M-cresol, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic solvent of 30mL is added to complete After fully dissolved, after be transferred in 100mL containers through organic solvent constant volume；

Preferably, in the step (2), the standard solution for preparing includes：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, 50mg M-cresol, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic solvent of 30mL is added to complete After fully dissolved, after be transferred in 100mL containers, through organic solvent constant volume, after take the obtained solution 10mL to 100mL containers In, through organic solvent constant volume as primary standard solution；After take in the primary standard solution 10mL to 100mL containers, through having Solvent constant volume is as secondary standard solution；Take secondary standard solution obtained above 1,2,5mL and primary standard molten respectively In liquid 1,2mL to 50mL containers, through organic solvent constant volume；Respectively obtain a concentration of 0.25g μ g/mL, 0.50 μ g/mL, 1.25 μ g/ The p- benzenediol standard solution of mL, 2.51 μ g/mL, 5.02 μ g/mL, 12.54 μ g/mL；A concentration of 0.07 μ g/mL, 0.13 μ g/ The m- benzenediol standard solution of mL, 0.34 μ g/mL, 0.67 μ g/mL, 1.34 μ g/mL, 3.35 μ g/mL；A concentration of 0.36 μ g/ The o- benzenediol standard solution of mL, 0.71 μ g/mL, 1.78 μ g/mL, 3.57 μ g/mL, 7.13 μ g/mL, 17.83 μ g/mL；Concentration For the phenol Standard solution of 0.26 μ g/mL, 0.53 μ g/mL, 1.32 μ g/mL, 2.64 μ g/mL, 5.28 μ g/mL, 13.19 μ g/mL； The m-cresol mark of a concentration of 0.14 μ g/mL, 0.28 μ g/mL, 0.71 μ g/mL, 1.42 μ g/mL, 2.83 μ g/mL, 7.08 μ g/mL Quasi- solution；A concentration of 0.24 μ g/mL, 0.48 μ g/mL, 1.21 μ g/mL, 2.42 μ g/mL, 4.85 μ g/mL, 12.12 μ g/mL O-cresol standard solution.

9. the detection method according to any one of claim 6 to 8, which is characterized in that the high-efficient liquid phase chromatogram condition Further include：

The chromatographic column column internal diameter 250mm × 4.6mm,

Preferably, the grain size of the filler is 5 μm；

Preferably, the chromatographic column column temperature：20-40 DEG C, preferably 30 DEG C；

Preferably, the chromatographic column column flow is 1.0ml/min；

Preferably, the sampling volume：10μL；

Preferably, the water and acetonitrile solution volume ratio are 50：50.

10. the detection method according to any one of claim 6 to 9, which is characterized in that described to heat the cigarette that do not burn Detection method includes the following steps for alcohol compound in main flume：

(1) test solution is prepared：

The total granules of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions, After the solution in described two series connection trapping bottles is vibrated 5min at room temperature afterwards, solution 2mL obtained above is pipetted, through 0.22 μm water phase membrane filtration；

(2) standard solution is prepared：

Take the o- benzenediol of 100mg, the p- benzenediol of 100mg respectively, the phenol of 100mg, the o-cresol of 50mg, 50mg M-cresol, the p-Cresol of 50mg, 20mg m- benzenediol be added into 50mL containers, the organic solvent of 30mL is added to complete After fully dissolved, after be transferred in 100mL containers, through organic solvent constant volume, after take the obtained solution 10mL to 100mL containers In, through organic solvent constant volume as primary standard solution；After take in the primary standard solution 10mL to 100mL containers, through having Solvent constant volume is as secondary standard solution；Take secondary standard solution obtained above 1,2,5mL and primary standard molten respectively In liquid 1,2mL to 50mL containers, through organic solvent constant volume；Respectively obtain a concentration of 0.25g μ g/mL, 0.50 μ g/mL, 1.25 μ g/ The p- benzenediol standard solution of mL, 2.51 μ g/mL, 5.02 μ g/mL, 12.54 μ g/mL；A concentration of 0.07 μ g/mL, 0.13 μ g/ The m- benzenediol standard solution of mL, 0.34 μ g/mL, 0.67 μ g/mL, 1.34 μ g/mL, 3.35 μ g/mL；A concentration of 0.36 μ g/ The o- benzenediol standard solution of mL, 0.71 μ g/mL, 1.78 μ g/mL, 3.57 μ g/mL, 7.13 μ g/mL, 17.83 μ g/mL；Concentration For the phenol Standard solution of 0.26 μ g/mL, 0.53 μ g/mL, 1.32 μ g/mL, 2.64 μ g/mL, 5.28 μ g/mL, 13.19 μ g/mL； The m-cresol mark of a concentration of 0.14 μ g/mL, 0.28 μ g/mL, 0.71 μ g/mL, 1.42 μ g/mL, 2.83 μ g/mL, 7.08 μ g/mL Quasi- solution；A concentration of 0.24 μ g/mL, 0.48 μ g/mL, 1.21 μ g/mL, 2.42 μ g/mL, 4.85 μ g/mL, 12.12 μ g/mL O-cresol standard solution；

(3) content of alcohol compound in the main flume for heating the cigarette that do not burn described in high effective liquid chromatography for measuring is used：

It takes standard solution and test solution to inject high performance liquid chromatograph to be measured, the high performance liquid chromatograph condition packet It includes：

Chromatographic column：Explosive E2 columns；

Mobile phase：Acetonitrile-aqueous solution；

Preferably, the chromatographic column column internal diameter 250mm × 4.6mm,

Preferably, the grain size of the filler is 5 μm；

Preferably, the chromatographic column column temperature：20-40 DEG C, preferably 30 DEG C；

Preferably, the chromatographic column column flow is 1.0ml/min；

Preferably, the sampling volume：10μL；

Preferably, the water and acetonitrile solution volume ratio are 50：50.

11. the detection method of free nicotine in a kind of main flume heating the cigarette that do not burn, which includes following step Suddenly：

(1) test solution is prepared；It includes obtaining trip from the total granules of the main flume for heating the cigarette that do not burn From nicotine；

(2) standard solution is prepared；

(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn；Wherein, The GC conditions include：

Chromatographic column：CP-1301 silicagel column capillary columns；

Column volume：30m×0.32mm×1.0μm.

12. detection method according to claim 11, which is characterized in that in the step (1), described to prepare test sample molten Liquid includes：

The total granules of cigarette is trapped under ISO suction modes using trapping solution, after by obtained solution filter disc vibrate, mistake Filter；

Wherein, the trapping solution is the mixed solution of water and chloroform, and the volume ratio of the water and chloroform is 1：1；

Preferably, the quantity of the cigarette be 3-7 branch, preferably 5；

Preferably, the duration of oscillation is 2-7min, preferably 5min；

Preferably, described be filtered into is filtered using anhydrous sodium sulfate syringe filters；

Preferably, in the step (1), the test solution for preparing includes：

Using trapping solution in ISO suction modes trap 5 cigarette total granules, after obtained solution is vibrated at room temperature 5min, preferably through the filtering of anhydrous sodium sulfate syringe filters, the quantity of the cigarette and the ratio of trapping solution are 5： 25ml；

Preferably, in the step (1), the test solution for preparing includes：

The total granules of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions, After the solution in described two series connection trapping bottles is vibrated 5min at room temperature afterwards, solution 2mL obtained above is pipetted, through anhydrous Sodium sulphate syringe filters filter.

13. detection method according to claim 11 or 12, which is characterized in that in the step (2), the preparation standard Solution includes：Nicotine standard product are taken, through organic solvent constant volume；

Preferably, the organic solvent is chloroform；

Preferably, in the step (2), the standard solution for preparing includes：

In the nicotine standard product to 50mL containers for weighing about 100mg respectively, the chloroform constant volume through 100mL；It pipettes above-mentioned molten Liquid is diluted through chloroform, obtain concentration be respectively 0.05mg/mL, 0.10mg/mL, 0.50mg/mL, 1.00mg/mL, The standard solution of 2.00mg/mL, 5.00mg/mL.

14. the detection method according to any one of claim 11 to 13, which is characterized in that the GC conditions are also Including：

Injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：20:1；

Carrier gas：Helium, preferable flow rate 1.2mL/min；

Preferably, the make-up gas flow velocity is 10mL/min；

Preferably, the dottle pin purging flow velocity is 10mL/min；

Preferably, 100 DEG C of the initial temperature keep 0.5min, rise to 200 DEG C by 100 DEG C with 20 DEG C/min rates, keep 1.5min。

15. the detection method according to any one of claim 11 to 13, which is characterized in that described to heat the cigarette that do not burn Main flume in free nicotine detection method includes the following steps：

(1) test solution is prepared：

The total granules of 5 cigarette is trapped under ISO suction modes using two series connection trapping bottles containing 25mL trapping solutions, After the solution in described two series connection trapping bottles is vibrated 5min at room temperature afterwards, solution 2mL obtained above is pipetted, through anhydrous Sodium sulphate syringe filters filter；

(2) standard solution is prepared：

In the nicotine standard product to 50mL containers for weighing about 100mg respectively, through chloroform constant volume；Above-mentioned solution is pipetted through trichlorine Methane dilute, obtain concentration be respectively 0.05mg/mL, 0.10mg/mL, 0.50mg/mL, 1.00mg/mL, 2.00mg/mL, 5.00mg/mL standard solution；

(3) gas chromatography is used to measure the content of alcohol compound in the main flume for heating the cigarette that do not burn：

It takes standard solution and test solution to inject gas chromatograph to be measured, the gas chromatograph condition includes：

Chromatographic column：CP-1301 silicagel column capillary columns；

Column volume：30m×0.32mm×1.0μm；

Preferably, injector temperature：250℃；

Detector temperature：275℃；

1 μ L of sample size；

The split ratio of split sampling：20:1；

Carrier gas：Helium, flow velocity 1.2mL/min；

Preferably, the make-up gas flow velocity is 10mL/min；

Preferably, the dottle pin purging flow velocity is 10mL/min；

Preferably, 100 DEG C of the initial temperature keep 0.5min, rise to 200 DEG C by 100 DEG C with 20 DEG C/min rates, keep 1.5min。