CN102072940B - Method for measuring contents of coumarin and safrole in flavor and fragrance for cigarette - Google Patents
Method for measuring contents of coumarin and safrole in flavor and fragrance for cigarette Download PDFInfo
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Abstract
The invention provides a method for measuring contents of coumarin and safrole in flavor and fragrance for cigarette, which comprises the steps of: first, dispersing coumarin and safrole in flavor and fragrance for cigarette in an aqueous solution and extracting with an organic reagent, sampling, filtering and performing instrument analysis and content measurement by using gas chromatography-mass spectrometry; selecting phenylethyl propionate as an internal standard substance and selecting ions of phenylethyl propionate, coumarin and safrole with mass to charge ratios m/z which are respectively 104, 146 and 162 in the mass spectrogram for quantitative analysis; and drawing a standard curve by using an internal standard method and fitting the sample with the standard curve to obtain the contents of coumarin and safrole. By adopting the method, coumarin and safrole in flavor and fragrance for cigarette are more completely extracted; and in the process of extraction, interfering materials can be removed to an extreme extent so that the sample spectrum is purified and pollution of samples to the injection port of the instrument and the chromatographic column is reduced, thereby the demand of sample detection in batches in actual work is met.
Description
Technical field
The present invention relates to measure cumarin and safrole Determination on content method, specifically be meant cumarin and safrole Determination on content method in the essence spice for cigarette.
Background technology
Cumarin and safrole have been proved to be animal body have been had extremely strong toxic and side effect at present, possibly cause inner visceral organ injury, even bring out cancer.Cumarin and safrole are mainly derived from plant.Essence spice for cigarette might be introduced cumarin and safrole in manufacturing process, consumer's health is caused potential threat.Therefore, be necessary the content of cumarin in the essence spice for cigarette and safrole is controlled.
With respect to the essence and flavoring agent of other types such as food and commodity, essence spice for cigarette has the characteristics of himself.The essence spice for cigarette complicated component, wide material sources are in a liquid state or the cream attitude more, and cumarin wherein and safrole are all water insoluble, are soluble in organic solvent.
At present, the sample treatment of cumarin and safrole has Direx process, ultrasonic extraction method, while distillation extraction method, steam distillation etc.All there is weak point in various degree in these pre-treating methods, and Direx process and ultrasonic extraction method are fast, but can extract more interfering material; Distillation extraction method and steam distillation workload are bigger, more consuming time simultaneously, and owing to used higher temperature in the extraction process, have the potential possibility of chemical substance loss.
Summary of the invention
The purpose of this invention is to provide cumarin and safrole Determination on content method in a kind of essence spice for cigarette; Can not only more fully extract cumarin and safrole in the essence spice for cigarette; And in extraction process, can greatly remove interfering material, the sample spectrogram is purified; Simultaneously also reduced the pollution of sample, can satisfy the needs that batch samples detects in the real work instrument injection port and chromatographic column.
The present invention provides cumarin and safrole Determination on content method in the essence spice for cigarette, may further comprise the steps:
1) extract preparation: get an amount of phenylethyl propionate, preparation contains the dichloromethane solution of phenylethyl propionate, as extract;
2) preparation of standard operation liquid: take by weighing cumarin and safrole; Dissolve constant volume in volumetric flask with extract; As standard reserving solution, standard reserving solution is contained the standard operation liquid that cumarin and safrole are respectively 1000ng/mL, 500ng/mL, 200ng/mL, 100ng/mL, 50ng/mL through stepwise dilution preparation;
3) processing of sample: the amount that adds the 5mL saturated sodium-chloride water solution according to every gram essence spice for cigarette; Get essence spice for cigarette and add saturated sodium-chloride water solution, vibration is dispersed in the saturated sodium-chloride water solution essence and flavoring agent; Add extract again; The volume ratio of saturated sodium-chloride water solution and extract is 1:2, fully leaves standstill after the vibration, treats to take off layer liquid filtering as treating test sample after the layering;
4) mensuration of sample: get 0.5 ~ 1 μ L and treat test sample; Inject gas chromatograph-mass spectrometer, phenylethyl propionate, cumarin and safrole are that 104,146,162 ions are quantitative with m/z respectively, use internal standard method drawing standard curve; Sample and typical curve match draw sample cumarin and safrole content.
The concentration of phenylethyl propionate is 100ng/mL in the said extract.
In step 3), can use hydro-extractor to accelerate the branch interval velocity during standing demix.
In step 4), the chromatographic condition of gas chromatograph-mass spectrometer: use nonpolar chromatographic column, carrier gas is a high-pure helium; Column flow rate is the 2mL/min constant current, does not shunt, and injector temperature is 320 ℃; Temperature programme is 70 ℃ of post initial temperatures, keeps 1min, rises to 160 ℃ with the speed of 10 ℃/min; Keep 0min, the speed with 40 ℃/min rises to 300 ℃ then, keeps 10min;
The mass spectrum condition of gas chromatograph-mass spectrometer: interface temperature is 280 ℃, and ion source temperature is 280 ℃, and the quadrupole rod temperature is 200 ℃; Ionizing energy is 70eV, and the solvent delay time is 6min, and time-event is to close detecting device in 12 minutes; The full scan mass range is 50-200amu; Select the ion monitoring pattern: the mass-to-charge ratio m/z of safrole is 162,135,131, and the mass-to-charge ratio m/z of phenylethyl propionate is 104,91,77, and the mass-to-charge ratio m/z of cumarin is 146,118,90.
Said nonpolar chromatographic column is DB-35MS.
The present invention is an object to be numbered 10712 sample (this sample does not detect safrole), has added the cumarin and the safrole of intermediate concentration, does the recovery of standard addition test, replicate determination 6 times, result such as table 1.
The recovery of table 1 method
The cumarin recovery is 82.6% ~ 110.7%, and mean value is 95.6%, and the safrole recovery is 94.4% ~ 103.2%, and mean value is 98.2%.With the precision of same testing result computing method, 6 results' relative standard deviation is respectively cumarin 5.6%, safrole 3.3%.Therefore, the present invention has method reappearance preferably, and accuracy is high, can satisfy the needs that batch samples detects in the real work.
Beneficial effect of the present invention: compare with direct liquid-liquid extraction method, the spectrogram background of liquid-liquid extraction method gained is lower indirectly, and peak shape is clean, and spectrogram is attractive in appearance.Because of in extraction process, can greatly remove interfering material, the sample that gets into instrument is purified, can reduce the pollution of sample to instrument injection port and chromatographic column, prolong instrument and easily-consumed products life-span.This method can more fully extract cumarin and the safrole in the essence spice for cigarette; Experimental result and Direx process basically identical; The method that calculates cumarin quantitatively is limited to 0.13mg/kg; The method of safrole quantitatively is limited to 0.09mg/kg, can satisfy the needs that batch samples detects in the real work.This method is simple to operate, and the result is reliable and stable rapidly, more is applicable to the detection of some difficult sample that disperses when Direx process is handled.
Description of drawings
Fig. 1 handles the TIC comparison diagram of same sample gained for direct liquid-liquid extraction method and indirect liquid-liquid extraction method.
The serve as reasons typical curve of safrole of standard operation solution gained of preparation of Fig. 2.
The serve as reasons typical curve of cumarin of standard operation solution gained of preparation of Fig. 3.
Embodiment
Below further specify the present invention through specific embodiment:
Embodiment 1
Reagent: methylene chloride, sodium chloride, phenylethyl propionate, cumarin, safrole, pure water.
Instrument: HP7890A-5975C gas chromatograph-mass spectrometer (GCMS) (U.S. Agilent company); AL204 electronic balance (precision 0.1mg, Mettler Toledo Inc.); Oscillator.
The chromatographic condition of gas chromatograph-mass spectrometer: chromatographic column: DB-35MS (30m * 0.32mm * 0.25 μ m); Carrier gas: high-pure helium; Column flow rate: 2mL/min constant current; Split ratio: do not shunt; Injector temperature: 320 ℃; Sample size: 1 μ L; Temperature programme: 70 ℃ of post initial temperatures, keep 1min, rise to 160 ℃ with the speed of 10 ℃/min, keep 0min, the speed with 40 ℃/min rises to 300 ℃ then, keeps 10min.
The mass spectrum condition interface temperature of gas chromatograph-mass spectrometer: 280 ℃; Ion source temperature: 280 ℃; Quadrupole rod temperature: 200 ℃; Ionization (EI) energy: 70eV; The solvent delay time: 6min; Time-event: closed detecting device in 12 minutes; Full scan mass range: 50 ~ 200amu; Select the ion monitoring pattern: the mass-to-charge ratio m/z of safrole is 162,135,131, and the mass-to-charge ratio m/z of phenylethyl propionate is 104,91,77, and the mass-to-charge ratio m/z of cumarin is 146,118,90.
The extract preparation: get phenylethyl propionate it is joined in the dichloromethane solution, preparation contains the dichloromethane solution of phenylethyl propionate 100ng/mL, as extract.
The preparation of standard operation liquid: take by weighing each 50mg of cumarin and safrole, dissolve constant volume in the 50mL volumetric flask, as standard reserving solution with extract.Standard reserving solution is contained the standard operation liquid that cumarin and safrole are respectively 1000ng/mL, 500ng/mL, 200ng/mL, 100ng/mL, 50ng/mL through stepwise dilution preparation.
The processing of sample: get 2.00 gram essence spice for cigarette; Add the 10mL saturated sodium-chloride water solution; Vibration is dispersed in the saturated sodium-chloride water solution essence and flavoring agent, adds the 20mL extract again; Fully leave standstill after the vibration, treat that taking off layer liquid after the layering crosses 0.22 μ m miillpore filter as treating test sample.When leaving standstill when being difficult to layering, can use hydro-extractor to accelerate the branch interval velocity.
Sample determination: get 1 μ L and treat test sample, inject gas chromatograph-mass spectrometer.The retention time deviation of sample and standard items is less than ± 0.1min.Qualitative ion: the mass-to-charge ratio m/z of safrole is 162,135,131, and the mass-to-charge ratio m/z of phenylethyl propionate is 104,91,77, and the mass-to-charge ratio m/z of cumarin is 146,118,90.Phenylethyl propionate, cumarin and safrole are that 104,146,162 ions are quantitative with mass-to-charge ratio m/z respectively.Use internal standard method drawing standard curve, sample and typical curve match draw sample cumarin and safrole content.
The standard operation liquid of 5 concentration gradients will preparing respectively gets into instrument; With phenylethyl propionate is interior mark; The curve that sets up standard was forced initial point; By the typical curve of safrole and the cumarin of the standard operation solution gained of preparation respectively like Fig. 2, shown in Figure 3, safrole y=0.3548x, related coefficient 0.99948; Cumarin y=0.2662x, related coefficient 0.99926.
Use this method to detect 18 essence and flavoring agent samples, each sample replicate determination twice, wherein two samples detect cumarin, and n.s. detects safrole, and not finding in the testing process has sample not to be suitable for this method.
Comparative Examples
Sample with same numbering is an experimental subjects; Use the pre-treating method of direct liquid-liquid extraction and indirect liquid-liquid extraction respectively; And use same instrument under same condition, to obtain two total ion currents (TIC) figure, with the comparison that is superimposed of two spectrograms, as shown in Figure 1.
The a spectrogram is the spectrogram of direct liquid-liquid extraction method sample preparation gained, and the b spectrogram is the spectrogram of indirect liquid-liquid extraction method sample preparation gained.Two kinds of methods are compared, and liquid-liquid extraction method spectrogram background is lower indirectly, and peak shape is clean, shows that this disposal route can make a large amount of interfering materials be retained in aqueous phase, and the sample that gets into instrument is purified, thereby common also more attractive in appearance.Meanwhile, purer sample also can reduce the pollution to instrument, prolongs instrument and easily-consumed products life-span.
Claims (6)
1. cumarin and safrole Determination on content method in the essence spice for cigarette may further comprise the steps:
1) extract is prepared: phenylethyl propionate is joined be mixed with extract in the dichloromethane solution;
2) preparation of standard operation liquid: take by weighing cumarin and safrole, in volumetric flask,, standard reserving solution is contained the standard operation liquid of cumarin and safrole through the stepwise dilution preparation as standard reserving solution with extract dissolving constant volume;
3) processing of sample: the amount that adds the 5mL saturated sodium-chloride water solution according to every gram essence spice for cigarette; Get essence spice for cigarette and add saturated sodium-chloride water solution, vibration is dispersed in the saturated sodium-chloride water solution essence and flavoring agent; Add extract again; The volume ratio of saturated sodium-chloride water solution and extract is 1:2, fully leaves standstill after the vibration, treats to take off layer liquid filtering as treating test sample after the layering;
4) mensuration of sample: get 0.5 ~ 1 μ L and treat test sample; Inject gas chromatograph-mass spectrometer; Select phenylethyl propionate, cumarin and the mass-to-charge ratio m/z of safrole in mass spectrogram to be respectively 104,146,162 ion and carry out quantitative test; Use internal standard method drawing standard curve, sample and typical curve match draw sample cumarin and safrole content.
2. according to cumarin in the said essence spice for cigarette of claim 1 and safrole Determination on content method, it is characterized in that: the concentration of phenylethyl propionate is 100ng/mL in the said extract.
3. according to cumarin in the said essence spice for cigarette of claim 1 and safrole Determination on content method, it is characterized in that: in step 3), use hydro-extractor to accelerate to divide interval velocity during standing demix.
4. according to cumarin in the said essence spice for cigarette of claim 1 and safrole Determination on content method, it is characterized in that: in step 3), take off layer liquid after the layering and use filtering with microporous membrane.
5. according to cumarin in the said essence spice for cigarette of claim 1 and safrole Determination on content method, it is characterized in that: in step 4), the chromatographic condition of gas chromatograph-mass spectrometer: use nonpolar chromatographic column, carrier gas is a high-pure helium; Column flow rate is the 2mL/min constant current, does not shunt, and injector temperature is 320 ℃; Temperature programme is 70 ℃ of post initial temperatures, keeps 1min, rises to 160 ℃ with the speed of 10 ℃/min; Keep 0min, the speed with 40 ℃/min rises to 300 ℃ then, keeps 10min;
The mass spectrum condition of gas chromatograph-mass spectrometer: interface temperature is 280 ℃, and ion source temperature is 280 ℃, and the quadrupole rod temperature is 200 ℃; Ionizing energy is 70eV, and the solvent delay time is 6min, and time-event is to close detecting device in 12 minutes; The full scan mass range is 50-200amu; Select the ion monitoring pattern: the mass-to-charge ratio m/z of safrole is 162,135,131, and the mass-to-charge ratio m/z of phenylethyl propionate is 104,91,77, and the mass-to-charge ratio m/z of cumarin is 146,118,90.
6. according to cumarin in the said essence spice for cigarette of claim 5 and safrole Determination on content method, it is characterized in that: said nonpolar chromatographic column is DB-35MS.
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Families Citing this family (10)
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| CN102253147B (en) * | 2011-07-19 | 2014-04-09 | 中国烟草总公司郑州烟草研究院 | Method for measuring content of dihydrocoumarin and 6-methyl coumarin in additive for tobaccos |
| CN102854278A (en) * | 2012-09-11 | 2013-01-02 | 鹰潭华宝香精香料有限公司 | Determination method of contents of coumarin and safrole in essence perfume |
| CN102998382B (en) * | 2012-10-17 | 2014-07-16 | 国家烟草质量监督检验中心 | Method for measuring contents of methanol, sec-butyl alcohol, sesamol and musk xylene in additive for cigarette |
| CN103869039B (en) * | 2014-04-08 | 2015-11-18 | 福建中烟工业有限责任公司 | A kind of method simultaneously detecting seven kinds of forbidding compounds in essence and flavoring agent |
| CN103983725B (en) * | 2014-05-22 | 2015-11-18 | 广西中烟工业有限责任公司 | The rapid assay methods of cumarin and safrole in a kind of essence and flavoring agent |
| CN103983714B (en) * | 2014-06-04 | 2015-10-14 | 吉林烟草工业有限责任公司 | A kind of method measuring cumarin and safrole content in tobacco product |
| CN108051517A (en) * | 2017-12-06 | 2018-05-18 | 中国烟草总公司郑州烟草研究院 | The automated detection method of cumarin in a kind of electronic cigarette liquid |
| CN108051516B (en) * | 2017-12-06 | 2020-07-28 | 中国烟草总公司郑州烟草研究院 | Automatic detection method for safrole in electronic cigarette liquid |
| CN108844932B (en) * | 2018-05-30 | 2020-10-30 | 中国烟草总公司郑州烟草研究院 | Time-resolved fluorescence immunochromatographic test strip for detecting safrole as well as preparation method and application thereof |
| CN108760924B (en) * | 2018-05-31 | 2021-04-20 | 河南中烟工业有限责任公司 | Method for extracting and detecting characteristic components of fragrant threads and popping beads of filter sticks |
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