CN102253147B - Method for measuring content of dihydrocoumarin and 6-methyl coumarin in additive for tobaccos - Google Patents
Method for measuring content of dihydrocoumarin and 6-methyl coumarin in additive for tobaccos Download PDFInfo
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- CN102253147B CN102253147B CN201110202329.2A CN201110202329A CN102253147B CN 102253147 B CN102253147 B CN 102253147B CN 201110202329 A CN201110202329 A CN 201110202329A CN 102253147 B CN102253147 B CN 102253147B
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- methylcoumarin
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Abstract
The invention discloses a method for measuring the content of dihydrocoumarin and 6-methyl coumarin in an additive for tobaccos. In the method, the content of the dihydrocoumarin and the 6-methyl coumarin in the additive for the tobaccos is measured directly by using a gas chromatograph-mass spectrometer (GC/MS), and the GC/MS analytical condition and the concentration range of the preparation of standard solution are optimized and selected in the measuring process according to the dihydrocoumarin and the 6-methyl coumarin. The method has the advantages of simple, convenient, quick and accurate operation, high sensitivity and repeatability. The detection limit of the dihydrocoumarin is 0.01 microgram/gram, and the detection limit of the 6-methyl coumarin is 0.01 microgram/gram; the average recovery rate of the dihydrocoumarin and the 6-methyl coumarin is 98.35 percent and 97.97 percent respectively, and the average relative standard deviation (RSD) of the dihydrocoumarin and the 6-methyl coumarin is 1.94 percent and 2.08 percent respectively.
Description
Technical field
The invention belongs to the physical and chemical inspection technical field of cigarette additive, relating generally to the assay method of dihydrocoumarin and 6-Methylcoumarin content in cigarette additive, is to adopt gas chromatograph-mass spectrometer (GCMS) (GC/MS) directly to measure the method for dihydrocoumarin and 6-Methylcoumarin content in cigarette additive specifically.
Background technology
In cigarette product design and process of manufacture, for improving product quality and meeting process requirements, enterprise often needs choosing to add adjuvants such as sweetener, antiseptic, humectant, combustion adjuvant, plastifier.The use of these adjuvants is one of important factor in order of cigarette product quality and security.
Dihydrocoumarin, colourless or light yellow thick liquid, or flaky crystal, have cumarin fragrance under room temperature, have nitrobenzene smell during high temperature, has pungent; For food, also, as the substitute of cumarin, be used as used for cosmetic essence; Modulation cream, coconut, Chinese cassia tree flavor essence; Also as flavouring essence for tobacco.6-Methylcoumarin, white plates crystal, has strong coconut fragrance, and fusing point: 73-76 ℃, is mainly used in preparing the type essence such as coconut, vanilla and caramel, for the preparation of organic synthesis, spices and cosmetics.
Have no at present the detection method bibliographical information of dihydrocoumarin and 6-Methylcoumarin in cigarette additive, and conventional trace analysis methods and results accuracy is lower, is not suitable for the assay of dihydrocoumarin and 6-Methylcoumarin in cigarette additive.
Summary of the invention
Object of the present invention is intended to overcome prior art defect, provides a kind of employing gas chromatograph-mass spectrometer (GCMS) (GC/MS) to measure the method for dihydrocoumarin and 6-Methylcoumarin content in cigarette additive simultaneously directly, improves speed, the accuracy measured.
In order to realize above object, the technical solution adopted in the present invention is: the assay method of dihydrocoumarin and 6-Methylcoumarin content in a kind of cigarette additive, comprises the following steps:
A, sample
Take cigarette additive sample, put into container and add dichloromethane solution and the anhydrous sodium sulfate that contains naphthalene, mechanical shaking extraction, gets supernatant and is sample extracting solution;
B, standard operation solution
Take dihydrocoumarin and 6-Methylcoumarin standard items, with the methylene chloride containing naphthalene, dissolve and constant volume, then further with the methylene chloride containing naphthalene, within the scope of 0.001-1.0 μ g/ml, dilute for thering is the standard operation solution of concentration gradient;
C, Gas Chromatography-Mass Spectrometry
The standard operation solution of variable concentrations gradient is injected respectively to GC/MS, with internal standard method, carry out the quantitative test of dihydrocoumarin and 6-Methylcoumarin content, with the chromatographic peak area of dihydrocoumarin and 6-Methylcoumarin and interior mark naphthalene, compare its respective concentration and carry out regretional analysis, obtain typical curve; Under the same conditions sample extracting solution is injected to GC/MS and measure, record the chromatographic peak area ratio of dihydrocoumarin and 6-Methylcoumarin and interior mark naphthalene, substitution typical curve, tries to achieve dihydrocoumarin and 6-Methylcoumarin content in sample;
Wherein GC/MS analysis condition is: chromatographic column: HP-VOC Fused-silica capillary column (60 mm i.d. * 1.8, m * 0.32 μ m d.f.); Injector temperature: 240 ℃, sample size: 1 μ L; Carrier gas: He, split ratio 10:1, flow velocity 1.5mL/min; Temperature programme: 80 ℃ of initial temperatures, with the speed of 15 ℃/min, rise to 245 ℃, keep 7min, to move 11min after 245 ℃ of posts; Transmission line temperature: 280 ℃; Ionization (El) energy: 70 eV; Ion source temperature: 230 ℃; Solvent delay 11 min, choice ion pattern (SIM) scanning, the selection ion of dihydrocoumarin is 148,120, and the selection ion of 6-Methylcoumarin is 160,131, and the selection ion of naphthalene is 128,102.
The concrete compound method with concentration gradient standard operation solution is: take respectively 0.0500g dihydrocoumarin and 6-Methylcoumarin, with the dichloromethane solution of naphthalene, dissolve and be settled to 100mL, be mixed with dihydrocoumarin and the 6-Methylcoumarin mother liquor of 500 μ g/mL, accurately pipette the dihydrocoumarin of different volumes and 6-Methylcoumarin mother liquor to 10mL volumetric flask, dichloromethane solution constant volume with naphthalene, be mixed with dihydrocoumarin and the 6-Methylcoumarin standard operation solution of variable concentrations, standard sequence: 0.001 μ g/mL, 0.005 μ g/mL, 0.010 μ g/mL, 0.050 μ g/mL, 0.10 μ g/mL, 0.50 μ g/mL, 1.00 μ g/mL, by taking 1.0 g additive samples, calculate, obtain standard sequence: 0.01 μ g/g, 0.05 μ g/g, 0.10 μ g/g, 0.50 μ g/g, 1.00 μ g/g, 5.00 μ g/g, 10.00 μ g/g.
In the dichloromethane solution of naphthalene, the concentration of naphthalene is 0.77 μ g/mL.
Anhydrous sodium sulfate dries 4h at 550 ℃ with front in muffle furnace.
Method of the present invention has overcome the deficiency of prior art sample treatment, for cigarette additive sample, has optimized sample-pretreating method and instrument testing conditions.Compared with prior art the inventive method has following excellent results:
Cigarette additive sample especially essence spice for cigarette be soluble perfume mostly, conventional solvent has water, ethanol, propylene glycol and glycerine, moisture in sample damages larger to capillary chromatographic column and GC/MS detection system, therefore experimental selection is usingd anhydrous sodium sulfate as drying agent, remove the moisture in sample.
(2) for the mensuration of dihydrocoumarin and 6-Methylcoumarin, prior art is quantitative mainly with external standard method, but for the larger cigarette additive sample of viscosity, with external standard standard measure, constant volume gets up cumbersome.And utilize inner mark method ration, by adding of internal standard compound, utilize the relative peak area value of component to carry out the calculating of some quantized datas, can be without constant volume, and can reduce the error of being brought by pre-treating method reappearance and instrument precision problem, therefore this law adopts inner mark method ration.The flavor component that in cigarette additive, tolerable adds is more, therefore its complicated component is difficult to select a suitable internal standard compound as object of reference, naphthalene has coal tar stink, can not be added in adjuvant, therefore the present invention selects naphthalene as interior mark.
(3) the inventive method has selected peak shape and the best HP-VOC post of separating effect as separating column, and adopts the GC/MS that can simultaneously provide quantitative and qualitative analysis information as detection mode, has guaranteed the accuracy of testing result.
(4) this method has advantages of easy and simple to handle, quick, accurate, highly sensitively and reproducible, and detecting of dihydrocoumarin is limited to 0.01 μ g/g, and detecting of 6-Methylcoumarin is limited to 0.01 μ g/g.The average recovery rate of dihydrocoumarin and 6-Methylcoumarin is respectively 98.35% and 97.97%, and average relative standard deviation (RSD) is respectively 1.94% and 2.08%.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of dihydrocoumarin and 6-Methylcoumarin assay method in cigarette additive of the present invention;
Fig. 2 is the chromatogram of standard solution, and in figure, X is naphthalene peak, and A is dihydrocoumarin peak, and B is 6-Methylcoumarin peak;
Fig. 3 is the chromatogram of sample solution, and in figure, X is naphthalene peak, and A is dihydrocoumarin peak, and B is 6-Methylcoumarin peak;
Fig. 4 is the canonical plotting of dihydrocoumarin in the specific embodiment of the invention;
Fig. 5 is the canonical plotting of 6-Methylcoumarin in the specific embodiment of the invention.
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
1. instrument and reagent:
Dihydrocoumarin and 6-Methylcoumarin, analyze pure; Naphthalene, analyzes pure; Anhydrous Na
2sO
4, analyze pure; Methylene chloride, chromatographic grade; Analytical balance, sensibility reciprocal: 0.0001 g; Horizontal cyclotron oscillation device; Gas chromatograph-mass spectrometer (GCMS) (GC/MS).
2. sample preparation:
Anhydrous sodium sulfate: with front in muffle furnace 550 ℃ dry 4h.
Get essence sample (cigarette additive) 1.00 g, accurately add the dichloromethane solution (concentration of naphthalene is 0.77 μ g/mL) of 10 mL naphthalenes, then add 5 g anhydrous sodium sulfates, vibration 30 min, standing 10 min, get supernatant and carry out GC/MS analysis.
3. standard solution configuration
Take respectively 0.0500g dihydrocoumarin and 6-Methylcoumarin, with the dichloromethane solution of naphthalene, dissolve and be settled to 100mL, be mixed with dihydrocoumarin and the 6-Methylcoumarin mother liquor of 500 μ g/mL, accurately pipette the dihydrocoumarin of different volumes and 6-Methylcoumarin mother liquor to 10mL volumetric flask, dichloromethane solution constant volume with naphthalene, be mixed with dihydrocoumarin and the 6-Methylcoumarin standard operation solution of variable concentrations, standard sequence: 0.001 μ g/mL, 0.005 μ g/mL, 0.010 μ g/mL, 0.050 μ g/mL, 0.10 μ g/mL, 0.50 μ g/mL, 1.00 μ g/mL, by taking 1.0 g essence samples, calculate, obtain accordingly standard sequence: 0.01 μ g/g, 0.05 μ g/g, 0.10 μ g/g, 0.50 μ g/g, 1.00 μ g/g, 5.00 μ g/g, 10.00 μ g/g.
4. Gas Chromatography-Mass Spectrometry:
The dihydrocoumarin of the variable concentrations preparing and 6-Methylcoumarin standard operation solution are injected to GC/MS, with dihydrocoumarin and 6-Methylcoumarin, compare its respective concentration ratio with the chromatographic peak area of interior mark naphthalene and carry out regretional analysis, obtain typical curve, as shown in table 1, as shown in Figure 4, the canonical plotting of 6-Methylcoumarin as shown in Figure 5 for the canonical plotting of dihydrocoumarin.Under the same conditions the sample after extracting is measured, record the chromatographic peak area ratio of dihydrocoumarin and 6-Methylcoumarin and interior mark naphthalene, substitution typical curve, dihydrocoumarin and the 6-Methylcoumarin content of trying to achieve in sample are respectively 1.32 μ g/g and 2.51 μ g/g.
GC/MS analysis condition is: chromatographic column: HP-VOC Fused-silica capillary column (60 mm i.d. * 1.8, m * 0.32 μ m d.f.); Injector temperature: 240 ℃, sample size: 1 μ L; Carrier gas: He, split ratio 10:1, flow velocity 1.5mL/min; Temperature programme: 80 ℃ of initial temperatures, with the speed of 15 ℃/min, rise to 245 ℃, keep 7min, to move 11min after 245 ℃ of posts; Transmission line temperature: 280 ℃; Ionization (El) energy: 70 eV; Ion source temperature: 230 ℃; Solvent delay 11 min, choice ion pattern (SIM) scanning, the selection ion of dihydrocoumarin is 148,120, and the selection ion of 6-Methylcoumarin is 160,131, and the selection ion of naphthalene is 128,102.
The typical curve of dihydrocoumarin and 6-Methylcoumarin in table 1 cigarette additive
Experimental example
1. the detection limit of the inventive method
The dihydrocoumarin of variable concentrations and 6-Methylcoumarin standard operation solution are injected to GC/MS, with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), calculate detection limit, detecting of dihydrocoumarin is limited to 0.01 μ g/g, and detecting of 6-Methylcoumarin is limited to 0.01 μ g/g.
2. the repeatability of the inventive method and recovery of standard addition
The standard solution that adds dihydrocoumarin and 6-Methylcoumarin in the cigarette additive sample that does not contain dihydrocoumarin and 6-Methylcoumarin, then carrying out respectively pre-treatment and GC/MS analyzes, and calculate its recovery according to adding scalar sum measured value, the results are shown in Table 2.As can be seen from Table 2, in 3 mark-on levels, the average recovery rate of dihydrocoumarin and 6-Methylcoumarin is respectively 98.35% and 97.97%, and average relative standard deviation (RSD) is respectively 1.94% and 2.08%, the recovery that the inventive method is described is higher, reproducible.
The recovery of table 2 dihydrocoumarin and 6-Methylcoumarin and repeatability (n=6)
Claims (4)
1. an assay method for dihydrocoumarin and 6-Methylcoumarin content in cigarette additive, is characterized in that: comprise the following steps:
A, sample
Take cigarette additive sample, put into container and add dichloromethane solution and the anhydrous sodium sulfate that contains naphthalene, mechanical shaking extraction, gets supernatant and is sample extracting solution;
B, standard operation solution
Take dihydrocoumarin and 6-Methylcoumarin standard items, with the methylene chloride containing naphthalene, dissolve and constant volume, then further with the methylene chloride containing naphthalene, within the scope of 0.001-1.0 μ g/ml, dilute for thering is the standard operation solution of concentration gradient;
C, Gas Chromatography-Mass Spectrometry
The standard operation solution of variable concentrations gradient is injected respectively to GC/MS analyser, with internal standard method, carry out the quantitative test of dihydrocoumarin and 6-Methylcoumarin content, with the chromatographic peak area of dihydrocoumarin and 6-Methylcoumarin and interior mark naphthalene, compare its respective concentration and carry out regretional analysis, obtain typical curve; Under the same conditions sample extracting solution is injected to GC/MS analyser and measure, record the chromatographic peak area ratio of dihydrocoumarin and 6-Methylcoumarin and interior mark naphthalene, substitution typical curve, tries to achieve dihydrocoumarin and 6-Methylcoumarin content in sample;
Wherein GC/MS analysis condition is: chromatographic column: HP-VOC Fused-silica capillary column; Injector temperature: 240 ℃, sample size: 1 μ L; Carrier gas: He, split ratio 10:1, flow velocity 1.5mL/min; Temperature programme: 80 ℃ of initial temperatures, with the speed of 15 ℃/min, rise to 245 ℃, keep 7min, to move 11min after 245 ℃ of posts; Transmission line temperature: 280 ℃; Ionizing energy: 70eV; Ion source temperature: 230 ℃; Solvent delay 11min, choice ion pattern scanning, the selection ion of dihydrocoumarin is 148,120, and the selection ion of 6-Methylcoumarin is 160,131, and the selection ion of naphthalene is 128,102.
2. assay method according to claim 1, it is characterized in that: the concrete compound method with concentration gradient standard operation solution is: take respectively 0.0500g dihydrocoumarin and 6-Methylcoumarin standard items, with the dichloromethane solution of naphthalene, dissolve and be settled to 100mL, be mixed with dihydrocoumarin and the 6-Methylcoumarin mother liquor of 500 μ g/mL, accurately pipette the dihydrocoumarin of different volumes and 6-Methylcoumarin mother liquor to 10mL volumetric flask, dichloromethane solution constant volume with naphthalene, be mixed with dihydrocoumarin and the 6-Methylcoumarin standard operation solution of variable concentrations, standard sequence: 0.001 μ g/mL, 0.005 μ g/mL, 0.010 μ g/mL, 0.050 μ g/mL, 0.10 μ g/mL, 0.50 μ g/mL, 1.00 μ g/mL, by taking 1.0g additive samples, calculate, obtain standard sequence: 0.01 μ g/g, 0.05 μ g/g, 0.10 μ g/g, 0.50 μ g/g, 1.00 μ g/g, 5.00 μ g/g, 10.00 μ g/g.
3. assay method according to claim 1, is characterized in that: in the dichloromethane solution of naphthalene, the concentration of naphthalene is 0.77 μ g/mL.
4. assay method according to claim 1, is characterized in that: anhydrous sodium sulfate dries 4h at 550 ℃ with front in muffle furnace.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393180A (en) * | 2008-10-30 | 2009-03-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring beta-naphthol content in additive agent for cigarette |
| CN102072940A (en) * | 2010-11-11 | 2011-05-25 | 中国烟草总公司湖北省公司 | Method for measuring contents of coumarin and safrole in flavor and fragrance for cigarette |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393180A (en) * | 2008-10-30 | 2009-03-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring beta-naphthol content in additive agent for cigarette |
| CN102072940A (en) * | 2010-11-11 | 2011-05-25 | 中国烟草总公司湖北省公司 | Method for measuring contents of coumarin and safrole in flavor and fragrance for cigarette |
Non-Patent Citations (4)
| Title |
|---|
| 李洁等.气相色谱质谱法测定化妆品中三种香豆素类物质的含量.《生命科学仪器》.2006,第4卷33-36. |
| 气相色谱-质谱法同时测定化妆品中5种香豆素类化合物;赵晓亚等;《分析试验室》;20100331;第29卷(第3期);76-79 * |
| 气相色谱质谱法测定化妆品中三种香豆素类物质的含量;李洁等;《生命科学仪器》;20060228;第4卷;33-36 * |
| 赵晓亚等.气相色谱-质谱法同时测定化妆品中5种香豆素类化合物.《分析试验室》.2010,第29卷(第3期),76-79. |
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