CN108680691A - The assay method of phthalic acid ester in essence spice for cigarette - Google Patents
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Abstract
Phthalic acid ester in a kind of essence spice for cigarette（PAEs）Assay method, it is characterised in that：Dispersion and preliminary extraction are carried out to sample using certain density ethanol water, then liquid-liquid extraction is carried out after liquid-liquid extraction layering to first extract using a certain proportion of n-hexane/ethyl acetate/isopropyl alcohol mixed solvent and takes supernatant liquor direct injection analysis.The method of the present invention can realize the fine dispersion of most of essence and flavoring agent samples just putting forward step, using n-hexane/ethyl acetate/isopropyl alcohol mixed solvent to first extract liquid-liquid extraction, the purification that can not only realize first extract, also can make the rate of recovery of 18 kinds of PAEs reach 90% or more.The glass apparatus that this method uses is also less, and due to the use of internal standard method, further simplifies solution transfer step, largely reduces the probability for polluting and bringing into pre-treatment, is suitble to the measurement of batch samples.
Description
Technical field
The invention belongs to cigarette additive harmful components physico-chemical analysis fields, are suitable for essence spice for cigarette（Liquid, paste
And emulsus）The measurement of middle phthalic acid ester.
Background technology
Flavouring essence for tobacco is one kind of food flavor.Essence is added in cigarette modulated process, can neutralize, correct or certain
The jealous and mouthfeel for changing tobacco in kind degree, achievees the effect that pleasure.But flavouring essence for tobacco is applied not only to tobacco perfuming,
Cigarette packaging material（Such as cigarette paper, filter stick etc.）On can also use, the smell demand for meeting consumer.It can be said that consumption
Person has very big chance to directly contact flavouring essence for tobacco when being consumed to cigarette product.Safety about flavouring essence for tobacco
Hygienic requirements is at present mainly also with reference to food flavor.
Phthalic acid ester（PAEs）It is one of controlled index of essence spice for cigarette safety and sanitation standard.But this standard is only
Define the Special migration of PAEs, limitation of the total amount also with reference to national standard about food flavor fragrance（<60mg/kg）.Cigarette is used
PAEs in essence largely derives from raw material, because certain PAEs can reduce the volatilization of fragrance matter；It is followed by fragrant
Essence transfer from other materials in storing transportational process obtains.PAEs is generally recognised as a kind of environmental hormone at present, in vivo
Long-term accumulation, human normal physiological function can be seriously affected, there are teratogenesis, the harm such as carcinogenic and mutagenesis.
About the measurement of phthalic acid ester in essence, the national standard method of associated recommendation is had no.In tobacco business about
Recommendation method is measured in flavouring essence for tobacco, but the method directly dilutes sample using ethyl alcohol, is measured, does not have using GC-MS
There is removal step, therefore there are many problems in use.On the one hand many essence or fragrance do not dissolve in ethyl alcohol（Such as some leachings
Cream）, another aspect is exactly perfume ingredient complexity, and direct injected can all have pollution to analytical column and ion source, and matrix is imitated
It should be apparent.The present invention improves the pre-treatment and analysis of existing method, is suitble to most of essence spice for cigarette at present
The measurement of middle PAEs.
Invention content
The purpose of the present invention adjacent benzene two in being based on above-mentioned prior art situation and a kind of essence spice for cigarette for proposing
The assay method of formic acid esters is mixed with essence and flavoring agent sample to be measured using ethanol water, is well being divided sample
While dissipating, the ingredient to be measured in sample is tentatively extracted；Then a certain proportion of n-hexane/ethyl acetate/different is used
Propanol solution carries out liquid-liquid extraction to just carrying solution, using gas-chromatography-mass spectrometry instrument（GC-MS）To PAEs therein
It is measured.
The purpose of the present invention is achieved through the following technical solutions：
Phthalic acid ester in a kind of essence spice for cigarette（PAEs）Assay method, including first to sample to be tested carry out before place
Reason, then pass through gas chromatography-mass spectrography（GC-MS）Technology is measured, and detailed process is as follows：
（1）Pre-treatment
It weighs in 0.3-0.6g essence and flavoring agents sample to 25 mL conical flask with stopper, accurately to 0.0001 g, 7-15mL ethyl alcohol is added
Aqueous solution, adds 250 μ L inner mark solutions, and ultrasonic extraction 30min takes 2mL just to carry in solution to 15mL glass centrifuge tubes, adds
Enter 5mL n-hexane/ethyl acetates/aqueous isopropanol, vortex oscillation 5min under conditions of 2000 rpm, after at 4000 revs/min
5min is centrifuged under the conditions of clock, takes supernatant liquor, it is to be measured.
（2）Blank assay
It is not added with sample, is repeated（1）Step.Due to phthalic acid ester generally existing in the environment, in all measurement PAEs
Pre-treatment in be both needed to measure blank, if containing a certain amount of PAEs in blank, cannot simply deduct, need strictly to search former
Cause avoids the introducing of PAEs in blank.
（3）Instrumental Analysis
It is measured using GC-MS, determination condition is as follows.
GC conditions：
Chromatographic column fixed phase：The methyl polysiloxane of 5% phenyl/95%；Specification：[30 m（Length）× 0.25 mm（Internal diameter）×
0.25 μm（Film thickness）].
Injector temperature：280℃；Sample size：1 μ L, split sampling（Split ratio：10:1）；Carrier gas：Helium（Purity >=
99.999%）, constant current mode, flow velocity：1.0 mL/min；Temperature program：60 DEG C of initial temperature keeps 1 min, with 20 DEG C/min
Rate to 220 DEG C, keep 1 min, then with the rate of 5 DEG C/min to 280 DEG C, keep 15 min.
Mass Spectrometry Conditions：
Ionization mode：Electron bombardment ionization source（EI）；Ionizing energy：70 eV；Transmission line temperature：280℃；Ion source temperature： 280℃
Or more；Quadrupole rod temperature：150℃；Mensuration mode：Select ion surveillance style（SIM）Scanning；Solvent delay：6 min.Respectively
Compound SIM conditions are shown in Table 1
（4）Deuterated-dibutyl phthalate is used in the present invention（Dibutyl phthalate-3,4,5,6-D4, No. CAS：
93952-11-5）As internal standard compound, purity >=99%, when use, is diluted using ethyl alcohol, a concentration of 0.1 mg/mL.
（5）A concentration of the 50% of ethanol water in the present invention is percent by volume；N-hexane/ethyl acetate/isopropanol
The volume ratio of solution is 3:1:1.
（6）Experiment should be all using glassware, after glassware used is cleaned, three times with level-one water wash, acetone leaching
1 h is steeped to toast 2 h at 200 DEG C after room temperature volatilization is dry, be cooled to room temperature spare.
（7）The configuration of standard solution and inner mark solution：
Mixed standard solution I：0.02 g is weighed respectively（It is accurate to 0.1 mg）Various PAEs standard items are placed in same 10 mL and hold
In measuring bottle, with n-hexane/ethyl acetate/isopropanol（3:1:1,V:V:V）Simultaneously constant volume is dissolved, is configured to a concentration of 2 mg/mL's
Mixed standard solution I.It is kept in dark place in 0 DEG C~4 DEG C refrigerators, the term of validity 6 months.
Mixed standard solution II：Accurately pipette 0.5 mL mixed standard solutions I, be placed in 10 mL volumetric flasks, with just oneself
Alkane/ethyl acetate/isopropanol（3:1:1,V:V:V）Constant volume is configured to the mixed standard solution II of a concentration of 0.1 mg/mL.In 0
DEG C~4 DEG C of refrigerators in be kept in dark place, the term of validity 6 months.
Standard working solution：The accurate mixed standard solution II for pipetting 25,50,100,250,500,750 μ L, is placed in respectively
25 mL volumetric flasks in, then accurately be added 250 μ L inner mark solutions, with n-hexane/ethyl acetate/isopropanol（3:1:1,V:V:V）Scale is settled to get series standard working solution.The series standard solution concentration of preparation is： 1、2、4、10、20、50
mg/kg。
Standard working solution is taken to carry out GC/MS analyses, ordinate is the quota ion peak area and internal standard of each analyte
The ratio of object quota ion peak area, abscissa are each analyte concentration, take at wherein at least 5 points, do the mark of each analyte
Quasi- working curve.18 kinds of PAEs are linear good in the concentration range of 1 ~ 50mg/kg, and related coefficient is from 0.9978-0.9999.
Experiment positive is chosen, carries out recovery of standard addition experiment, mark-on amount is respectively 2,10,40 mg/kg, each
Equal parallel determination 5 times, are averaged in mark-on level, and calculate the opposite mean standard deviation of 5 parallel determinations（RSD）, by
This obtains average recovery rates and RSD of 18 kinds of PAEs in different mark-on levels, and concrete outcome is shown in Table 2.
Can be obtained by table 2, rate of recovery ranges of 18 kinds of PAEs under the conditions of basic, normal, high 3 each mark-on 90.2 ~ 105.8%,
The rate of recovery is good；Average RSD is respectively less than 8%, and it is good to measure precision.
Experiment positive is chosen, mark-on is carried out with the minimum cup concentration of standard curve, replication 10 times is calculated and measured
As a result SD, using 3SD and 10SD as the detection limit of method（LOD）And quantitative limit（LOQ）, the results are shown in Table 3.
（8）Advantage existing for the present invention and explanation：
Using 50%（Percent by volume）Ethanol solution dispersion and preliminary extraction are carried out to sample to be tested, relative to existing mark
Sample is extracted using ethyl alcohol in standard, most of sample dispersions obtain more preferably.This is because essence and flavoring agent is dissolved in water a bit
Insoluble in ethyl alcohol, and some are dissolved only in ethyl alcohol, and also a few sample is that second alcohol and water is all insoluble, using 50% ethyl alcohol
Solution（The ratio of second alcohol and water is 1:1）Dispersing and dissolving is carried out to sample, most of essence and flavoring agent samples may be implemented in practice
The excellent dissolution of product, this just plays better peptizaiton, and the destruction for being equivalent to matrix is more thorough, and ingredient to be measured can be more
Good dissolution.
Liquid liquid extraction is carried out to ethanol water using n-hexane/ethyl acetate/isopropyl alcohol mixed solvent of special ratios
It takes, relative to directly ethyl alcohol being used to extract sample introduction in current standard, there are except impurity and protect the double effects of analytical instrument.This
Be because, liquid-liquid extraction layering, ethanol water in lower layer, n-hexane/ethyl acetate/isopropanols of special ratios on upper layer,
This step is equivalent to a purifying step, and many chaff interferents are not all extracted in final sample introduction solution in essence, are played
A degree of clean-up effect（Specifically see Fig. 3-Fig. 5）；On the other hand, due to n-hexane/ethyl acetate/aqueous isopropanol polarity
It is weak compared with ethyl alcohol, therefore, it is more suitable for the sample introduction requirement of nonpolar analytical column.Cleaner, the weaker sample introduction solution of polarity can be with bigger
That changes avoids analytical column and ion source from being contaminated.
Use volume ratio for 3:1:1 n-hexane/ethyl acetate/aqueous isopropanol carries out liquid liquid extraction to just carrying solution
It takes, the measurement rate of recovery of 18 kinds of PAEs to be measured can be made to be above 90%.This is because there is document report Cigarette paper before
The measurement of middle PAEs is to adopt to be soaked in water, and ethyl alcohol just carries, and carries out liquid-liquid extraction using n-hexane afterwards（Tang Gangling, Bian Zhaoyang, poplar
Fly, waits measurement [J] tobaccos of cigarette tipping papers, internal lining paper and tobacco shred and 18 kinds of phthalic acid esters in box packaging paper
Science and technology, 2012（9）：36-40.）, since DMP the and DEP carbochains in PAEs be all very short, there is certain polarity, all have in water
There is certain solubility, therefore, solubility is poor in n-hexane, and extraction efficiency is very low（Zhang Zeming, Zhang Honghai, Li Jianlong,
Equal solid phase microextraction-gas chromatography-mass spectrography measures seawater and phthalate pollutant [J] points in deposit
Analysis chemistry, 2017,45（3）：348-356.）；And for the weaker compound of DEHP and DNP isopolarities, only in n-hexane
Just there is best dissolubility, use volume ratio for 3:1:1 n-hexane/ethyl acetate/aqueous isopropanol, may be implemented 18 kinds
The better extract of ingredient, the rate of recovery of mark-on sample all the components can reach 90% and on（It is shown in Table 2）.
In the assay, ion source temperature is set as 280 DEG C or more, it is possible to prevente effectively from impurity is for ion source
Pollution.Many methods are arranged to operate, more such as Agilent instrument ion source temperature all in accordance with the ordinary temperature of ion source now
Conventional is set as 230 DEG C, and ion source temperature, in fact, PAEs are not also all emphasized in the standard method for much measuring PAEs
Class compound is easy to contaminated ion source, especially under the conditions of sample purification is incomplete.Ion source temperature is improved, can be incited somebody to action
Sample ionization is more complete, reduces the cleaning frequency of ion source.
Description of the drawings
Fig. 1 is the chromatogram of Plays solution of the present invention；
In the figure：1-DMP 2-DEP 3-DAP 4-DIBP 5-DBP 6-DMEP 7-BMPP 8-DEEP 9-DPP 10-DHXP
11-BBP 12-DBEP 13-DCHP 14-DEHP 15- diphenyl phthalate 16-DNOP 17-DINP 18-DNP IS-
Internal standard.
Fig. 2 is the chromatogram that mark-on sample measures in the present invention,
In the figure：1-DEP 2-DAP 3-DBP IS- internal standards.
Fig. 3 recommends the selection ion spectrogram of method measurement same sample DIBP in method and the present invention using industry,
Wherein A is industry recommendation method, and B is method in the present invention.
Fig. 4 recommends the selection ion spectrogram of method measurement same sample DBP in method and the present invention using industry,
Wherein A is industry recommendation method, and B is method in the present invention.
Fig. 5 recommends method in method and the present invention to measure the deuterated DBP of same sample using industry（Internal standard）Selection ion
Spectrogram,
Wherein A is industry recommendation method, and B is method in the present invention.
Specific implementation mode
The present invention is described further with reference to embodiments：
Embodiment：The measurement of phthalic acid ester in essence spice for cigarette sample.
（1）Pre-treatment
It weighs in 0.3-0.6g essence and flavoring agents sample to 25 mL conical flask with stopper, accurately to 0.0001 g, 7-15mL ethyl alcohol is added
Aqueous solution（Volume ratio is 1:1）, add 250 μ L inner mark solutions（Solvent is ethyl alcohol, a concentration of 0.1 mg/mL）, ultrasonic extraction
30min takes 2mL just to carry in solution to 15mL glass centrifuge tubes, and 5mL n-hexane/ethyl acetates/aqueous isopropanol is added（Volume
Than being 3:1:1）, vortex oscillation 5min under conditions of 2000 rpm, after centrifuge 5min under the conditions of 4000 revs/min, take
Layer clear liquid, it is to be measured.
（2）Blank assay
It is not added with sample, is repeated（1）Step.
（3）Instrumental Analysis
It is measured using GC-MS, determination condition is as follows.
GC conditions：
Chromatographic column fixed phase：The methyl polysiloxane of 5% phenyl/95%；Specification：[30 m（Length）× 0.25 mm（Internal diameter）×
0.25 μm（Film thickness）].
Injector temperature：280℃；Sample size：1 μ L, split sampling（Split ratio：10:1）；Carrier gas：Helium（Purity >=
99.999%）, constant current mode, flow velocity：1.0 mL/min；Temperature program：60 DEG C of initial temperature keeps 1 min, with 20 DEG C/min
Rate to 220 DEG C, keep 1 min, then with the rate of 5 DEG C/min to 280 DEG C, keep 15 min.
Mass Spectrometry Conditions：
Ionization mode：Electron bombardment ionization source（EI）；Ionizing energy：70 eV；Transmission line temperature：280℃；Ion source temperature： 280℃
Or more；Quadrupole rod temperature：150℃；Mensuration mode：Select ion surveillance style（SIM）Scanning；Solvent delay：6 min.Respectively
Compound SIM conditions are shown in Table 1.
4）The preparation of standard solution
Mixed standard solution I：0.02 g is weighed respectively（It is accurate to 0.1 mg）Various PAEs standard items are placed in same 10 mL and hold
In measuring bottle, with n-hexane/ethyl acetate/isopropanol（3:1:1,V:V:V）Simultaneously constant volume is dissolved, is configured to a concentration of 2 mg/mL's
Mixed standard solution I.It is kept in dark place in 0 DEG C~4 DEG C refrigerators, the term of validity 6 months.
Mixed standard solution II：Accurately pipette 0.5 mL mixed standard solutions I, be placed in 10 mL volumetric flasks, with just oneself
Alkane/ethyl acetate/isopropanol（3:1:1,V:V:V）Constant volume is configured to the mixed standard solution II of a concentration of 0.1 mg/mL.In 0
DEG C~4 DEG C of refrigerators in be kept in dark place, the term of validity 6 months.
Standard working solution：The accurate mixed standard solution II for pipetting 25,50,100,250,500,750 μ L, is placed in respectively
25 mL volumetric flasks in, then accurately be added 250 μ L inner mark solutions, with n-hexane/ethyl acetate/isopropanol（3:1:1,V:V:V）Scale is settled to get series standard working solution.The series standard solution concentration of preparation is： 1、2、4、10、20、50
mg/kg。
5）Take standard working solution carry out GC/MS analyses, ordinate be each analyte quota ion peak area with it is interior
The ratio of object quota ion peak area is marked, abscissa is each analyte concentration, takes at wherein at least 5 points, does each analyte
Standard working curve.It is obtained by the content of ingredient to be measured in essence spice for cigarette according to standard curve.With parallel determination twice
Average value is final measurement result, is accurate to 1 mg/kg.
Concrete outcome is shown in Table 4 in this example, and chromatogram is shown in attached drawing 2.
4 sample size of table
Claims (5)
1. phthalic acid ester in a kind of essence spice for cigarette（PAEs）Assay method, including first to sample to be tested carry out before
Processing, then pass through gas chromatography-mass spectrography（GC-MS）Technology is measured, it is characterised in that：The pretreatment process is：
It is carried at the beginning of first being disperseed to sample using ethanol water, then liquid-liquid extraction, specific mistake is carried out to first extract using mixed solvent
Journey is as follows：
It weighs in 0.3-0.6g essence and flavoring agents sample to 25 mL conical flask with stopper, accurately to 0.0001 g, 7-15mL ethyl alcohol is added
Aqueous solution, adds 250 μ L inner mark solutions, and ultrasonic extraction 30min takes 2mL just to carry in solution to 15mL glass centrifuge tubes, adds
Enter 5mL n-hexane/ethyl acetates/aqueous isopropanol, vortex oscillation 5min under conditions of 2000 rpm, after at 4000 revs/min
5min is centrifuged under the conditions of clock, takes supernatant liquor, carries out GC-MS measurement；Every batch of does blank test, that is, is not added with sample, repeats
Above-mentioned steps.
2. phthalic acid ester in essence spice for cigarette according to claim 1（PAEs）Assay method, feature exists
In：Internal standard uses deuterated-dibutyl phthalate, and a concentration of 0.1 mg/mL, solvent is ethyl alcohol.
3. phthalic acid ester in essence spice for cigarette according to claim 1（PAEs）Assay method, feature exists
In：A concentration of the 50% of the ethanol water is percent by volume；The volume ratio of n-hexane/ethyl acetate/aqueous isopropanol
Example is 3:1:1.
4. phthalic acid ester in essence spice for cigarette according to claim 1（PAEs）Assay method, feature exists
In：GC-MS instrumental conditions are as follows：
GC conditions：
Chromatographic column fixed phase：The methyl polysiloxane of 5% phenyl/95%；Specification：30 m× 0.25 mm× 0.25 μm
Injector temperature：280℃；Sample size：1 μ L, split sampling, split ratio：10:1；Carrier gas：Helium, constant current mode, stream
Speed：1.0 mL/min；Temperature program：60 DEG C of initial temperature keeps 1 min, with the rate of 20 DEG C/min to 220 DEG C, keeps 1
Min, then with the rate of 5 DEG C/min to 280 DEG C, keep 15 min；
Mass Spectrometry Conditions：
Ionization mode：Electron bombardment ionization source（EI）；Ionizing energy：70 eV；Transmission line temperature：280℃；Ion source temperature： 280℃
Or more；Quadrupole rod temperature：150℃；Mensuration mode：Select ion surveillance style（SIM）Scanning；Solvent delay：6 min；Respectively
Compound SIM conditions are shown in Table 1：
。
5. phthalic acid ester in essence spice for cigarette according to claim 1（PAEs）Assay method, feature exists
In：GC-MS measurement in, first prepare phthalic acid ester standard solution, standard solution using n-hexane/ethyl acetate/
Isopropanol（3:1:1,V:V:V）It prepares, concentration is respectively 1,2,4,10,20,50 mg/kg.
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| CN110887912A (en) * | 2019-12-19 | 2020-03-17 | 广西中烟工业有限责任公司 | Method for detecting phthalic acid ester in tobacco essence or water-based adhesive |
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| CN108680691B (en) | 2020-06-19 |
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