CN110487924B - Method for detecting cigarette perfuming uniformity based on additional marker - Google Patents
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Abstract
本发明提供一种基于外加标记物的卷烟加香均匀性的检测方法，包括：将苯乙醇酸酯类化合物作为外加标记物加入烟用香精中，含有外加标记物的烟用香精经加香工序添加到烟丝上，将加香后不同批次的烟丝平衡、研磨、过筛后进行加速溶剂萃取，分别获得不同批次烟丝的萃取液，再分别将萃取液进行气相色谱串联质谱法分析，获得多个萃取液中外加标记物的含量，进而计算获得卷烟的加香均匀性。本发明提供的一种基于外加标记物的卷烟加香均匀性的检测方法，选择香精和烟丝组分以外的化合物作为外加标记物，能更加客观、科学地准确量化评价卷烟加香工序的均匀性，对于制丝工艺评价、稳定产品质量具有非常重要的意义。The invention provides a method for detecting the uniformity of cigarette flavoring based on an external marker. Add to cut tobacco, balance, grind and sieve different batches of cut tobacco after flavoring, and then perform accelerated solvent extraction to obtain extracts of different batches of cut tobacco, respectively, and then analyze the extracts by gas chromatography tandem mass spectrometry to obtain The content of the added markers in multiple extracts was calculated to obtain the uniformity of cigarette flavoring. The invention provides a method for detecting the uniformity of cigarette aromatization based on an external marker. Compounds other than flavor and tobacco cut components are selected as the external marker, which can more objectively, scientifically and accurately quantitatively evaluate the uniformity of the cigarette flavoring process. It is of great significance for the evaluation of the silk making process and the stability of the product quality.
Description
Technical Field
The invention belongs to the technical field of tobacco performance evaluation, and relates to a cigarette flavoring uniformity detection method based on an additional marker.
Background
Through comprehensive literature research, some reports on quantitative research on uniformity of feeding and flavoring processes in the tobacco industry and outside in recent years are found, wherein most of the reports select one or a few essence components as markers.
The invention patent with the application number of 201210172531.X discloses a feeding uniformity evaluation method for detecting burley tobacco processing based on xylitol, wherein the chemical component representing uniformity is determined to be xylitol through analysis of chemical components of tobacco leaves before and after burley tobacco feeding, and the xylitol is used as an analysis target component to be quantitatively analyzed.
The invention patent with application number 201310052198.3 discloses a method for evaluating cigarette shred preparation charging uniformity based on characteristic fragrance substances, which is characterized in that the characteristic fragrance substances suitable for representing uniformity are screened out, ethyl maltol is used as a marker, the distribution condition of feed liquid content in a product is represented by the content of the marker in the product after charging, and the uniformity degree of a charging process is determined through detection, calculation and statistical analysis.
The invention patent with the application number of 201410155486.6 provides a method for determining the feeding uniformity of cigarette cut tobacco based on multi-index characteristic substance empowerment, which inspects characteristic components such as propylene glycol, ethyl maltol, menthol, key ethyl ester in extract and the like, takes the contribution degree of the characteristic components to the quality of cigarettes as weight, and adopts a weighted average method to calculate the effective distribution condition of feed liquid in the cut tobacco making and feeding process so as to quantify the feeding uniformity of the cigarette cut tobacco.
The invention patent with application number 200810022416.8 relates to a method for detecting cigarette perfuming uniformity based on a marker, menthol is used as the marker, and the standard deviation of the content of the marker after perfuming is utilized to reflect the perfuming uniformity.
The invention patent with application number 200910227567.1 discloses a method for measuring feed liquid application uniformity in a cigarette feeding process, which takes 1, 2-propylene glycol in the feed liquid as a marker, uses the content of the 1, 2-propylene glycol in the fed tobacco flakes to represent the distribution condition of the feed liquid content in the tobacco flakes, and determines the uniformity degree of feeding through detection, calculation and statistical analysis.
The above patent documents all select one or a few essence or liquid components as markers to characterize the uniformity of the flavoring and casing process. Part of markers exist in the cut tobacco in a small amount and interfere uniformity evaluation; and the other part of markers do not exist in the cut tobacco, but only one marker is not enough to perfect and systematically evaluate the uniformity of the cigarette flavoring process.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for detecting the cigarette flavoring uniformity based on an additional marker, which selects a proper additional characteristic marker as a characterization object, adopts ASE to pretreat a sample, quantitatively determines the marker in the flavored cut tobacco through GC-MS/MS, and further evaluates the uniformity of the cigarette flavoring process.
In order to achieve the above objects and other related objects, the present invention provides a method for detecting cigarette flavoring uniformity based on an additional marker, comprising: adding a phenylglycollate compound serving as an external marker into tobacco essence, adding the tobacco essence containing the external marker into tobacco shreds through a flavoring process, balancing, grinding and screening the flavored tobacco shreds in different batches, performing Accelerated Solvent Extraction (ASE) to respectively obtain extraction liquid of the tobacco shreds in different batches, performing gas chromatography tandem mass spectrometry (GC-MS/MS) analysis on the extraction liquid to obtain the content of the external marker in a plurality of extraction liquid, and further calculating to obtain the flavoring uniformity of the cigarettes.
Preferably, the flavoring process is a process of spraying tobacco essence into the cut tobacco of the cigarette.
Preferably, the phenethyl alcohol ester compound is selected from one or more of phenylethyl formate, phenylethyl acetate, phenylethyl propionate, phenylethyl butyrate and phenylethyl phenylacetate.
More preferably, the phenethyl alcohol ester compound comprises phenethyl formate, phenethyl acetate, phenethyl propionate, phenethyl butyrate and phenethyl phenylacetate.
The selection principle of the mandelic ester compound as an external marker is as follows: a) the added marker is not present in cigarette essence or tobacco shreds and can not be introduced in the production process. b) The added marker has stable physicochemical property, and is easy to extract and perform qualitative and quantitative analysis. c) The structure and the property of the added marker are similar to various characteristic aroma components in the cigarette essence, and the cigarette aroma style is not influenced.
Preferably, the addition concentration of the individual mandelate compounds is 300-500 mg/mL. More preferably, the concentration of the individual mandelate compounds added is 400 mg/mL.
Preferably, the sampling interval time of the cut tobaccos of different batches is 0.9-1.1 min. More preferably, the sampling interval time of the cut tobaccos of different batches is 1.0 min.
Preferably, the sampling amount of the cut tobacco of different batches is 90-110 g/time. More preferably, the amount of the cut tobacco of the different batches sampled is 100 g/time.
Preferably, the equilibrium conditions are: the equilibrium temperature is 20 +/-2 ℃; the equilibrium relative humidity is 60 +/-5%; the balance time is 22-26 h. More preferably, the equilibrium conditions are: the equilibrium temperature is 20 +/-1 ℃; the equilibrium relative humidity is 60 +/-3%; the equilibration time was 24 h.
Preferably, the grinding is to a fine powder.
Preferably, the screened mesh size is 38-42 mesh. More preferably, the screened mesh size is 40 mesh.
Preferably, the screened tobacco shred sample is ground and uniformly mixed with diatomite before the accelerated solvent extraction.
More preferably, the mass ratio of the tobacco shred sample to the diatomite is 3.9-4.1: 1. Further preferably, the mass ratio of the tobacco shred sample to the diatomite is 4: 1.
Preferably, the processing conditions for accelerating solvent extraction are: the extraction solvent is selected from one of methanol, isopropanol, acetonitrile, n-hexane, dichloromethane or ethyl acetate; the extraction temperature is as follows: 60-140 ℃; static extraction time: 3-25 min; cycle number: 1-3 times; extraction pressure: 10-10.5 MPa; heating time: 3-7 min; leaching volume: 55-65 percent; nitrogen purging time: 45-75 s.
More preferably, the process conditions for accelerated solvent extraction are: extracting solvent: n-hexane; the extraction temperature is as follows: 100 ℃; static extraction time: 5 min; cycle number: 2 times; extraction pressure: 10.34 MPa; heating time: 5 min; leaching volume: 60 percent; nitrogen purging time: for 60 s.
Preferably, an internal standard solution is added when the solvent extraction is accelerated, and the internal standard solution is an aqueous solution of benzyl acetate.
More preferably, the mass ratio of the benzyl acetate in the benzyl acetate water solution to the tobacco shred samples is 0.9-1.1: 400000. Further preferably, the mass ratio of the benzyl acetate in the benzyl acetate aqueous solution to the tobacco shred samples is 1: 400000.
Preferably, the accelerated solvent extraction is followed by filtration with a filter membrane. More preferably, the filter membrane has a gauge of 0.45 μm.
Preferably, in the gas chromatography tandem mass spectrometry (GC-MS/MS), the determination conditions of the gas chromatography are:
a chromatographic column: HP-5MS capillary column (30 m.times.0.25 mm.times.0.25 μm); sample inlet temperature: 280 ℃ and 300 ℃, preferably 290 ℃; sample introduction amount: 0.5-2.0. mu.L, preferably 1.0. mu.L; carrier gas: high-purity helium, wherein the purity of carrier gas is more than or equal to 99.999 percent; flow rate of carrier gas: 0.5-1.5ml/min, preferably 1.0 ml/min; the split ratio is as follows: 10: 1; temperature rising procedure: the initial temperature was maintained at 60 ℃ for 2min and increased to 280 ℃ at a rate of 5 ℃/min for 10 min.
Preferably, in the gas chromatography tandem mass spectrometry (GC-MS/MS), the determination conditions of the mass spectrum are as follows:
an ionization mode: an Electron Impact (EI) ion source; ionization energy: 70 eV; ion source temperature: 250 ℃ and 270 ℃, preferably 260 ℃; quadrupole temperature: 140 ℃ to 160 ℃, preferably 150 ℃; transmission line temperature: 270 ℃ and 290 ℃, preferably 280 ℃; the scanning mode is as follows: MS1 Scan Scan, Product ion Scan, MRM Scan; and (3) data acquisition mode: MRM; and (3) spectrogram retrieval: NIST spectral library.
Preferably, the additional label is quantified using an internal standard curve method.
More preferably, the internal standard curve method comprises the steps of:
A) taking a standard substance of a mandelate compound, adding ethanol for gradual dilution, and then adding an internal standard solution to prepare a series of standard working solutions with different concentrations;
B) respectively carrying out GC-MS/MS analysis on a series of standard working solutions with different concentrations in the step A) to obtain a linear relation between the chromatographic peak area ratio of various mandelate compounds/internal standards and the concentration ratio of the corresponding mandelate compounds/internal standards, drawing corresponding standard working curves, and calculating to obtain regression equations of the standard working curves of the various mandelate compounds;
C) and C, performing GC-MS/MS analysis on the extract, substituting the obtained chromatographic peak area ratio of various mandelic ester compounds and the internal standard into a regression equation of the standard working curve of the corresponding mandelic ester compound in the step B), and calculating the content of the corresponding mandelic ester compound in the sample solution according to the known concentration of the internal standard.
Further preferably, in the step a), the standard working solution is a mixed stock solution obtained by adding ethanol to the standard substance of the mandelate compound and diluting the standard substance step by step, adding an internal standard solution, and adding ethanol to dissolve and fix the volume.
Still more preferably, the mixed stock solution comprises a primary mixed stock solution and a secondary mixed stock solution, wherein the concentration of each mandelic ester compound in the primary mixed stock solution is 10000 mug/mL, and the concentration of each mandelic ester compound in the secondary mixed stock solution is 100 mug/mL. The first-stage mixed stock solution and the second-stage mixed stock solution are both obtained by adding ethanol into a standard substance of the phenylglycolate compound and diluting the standard substance step by step.
Most preferably, the mixed stock solution is stored in a refrigerator at 4 ℃.
Further preferably, in step A), the concentration of each mandelate-based compound in the standard working solution is 0.10 to 10.00. mu.g/mL.
Further preferably, in step a), the internal standard solution is an aqueous solution of benzyl acetate.
Still more preferably, in the standard working solution, the ratio of the added mass of benzyl acetate to the added mass of the mandelic acid ester compound in the internal standard solution is 50: 5-500.
Further preferably, in step B) or C), the standard working curve has a ratio of the areas of the chromatographic peaks of the various mandelic ester compounds to the internal standard as ordinate (Y-axis) and a ratio of the concentrations of the corresponding mandelic ester compounds to the internal standard as abscissa (X-axis).
Preferably, the perfuming uniformity of the cigarettes is calculated according to formulas (1) and (2), wherein the formula (1) is used for calculating the standard deviation of the content of the additional markers in the perfumed cigarette samples of different batches, the formula (2) is used for calculating the variation coefficient of the content of the additional markers in the perfumed cigarette samples of different batches,
the formula (1) is:
the formula (2) is:
in the formula: SDiIs the standard deviation of the i-th applied marker content;
Sirthe amount of the ith additional marker in the sample of the batch r;
n is the batch of samples;
CVithe coefficient of variation of the i-th additional marker content.
The standard deviation SDiValue and coefficient of variation CViThe value comprehensively reflects the uniformity degree of the added markers with different boiling points in the cigarette flavoring process, SDiValue and CViThe smaller the value, the better the uniformity.
As described above, the method for detecting the cigarette perfuming uniformity based on the additional marker provided by the invention selects a proper additional characteristic marker as a characterization object, quantitatively adds the additional characteristic marker into tobacco essence, adds the additional characteristic marker into tobacco shreds through a perfuming process, pre-treats the sample by using ASE, quantitatively determines the marker in the flavored tobacco shreds through GC-MS/MS, and further evaluates the uniformity of the cigarette perfuming process. Has the following beneficial effects:
(1) aiming at the current situation that essence or feed liquid components are usually selected as markers in the existing documents, but the markers are partially present in tobacco shreds and easily interfere the detection result, the method for detecting the cigarette perfuming uniformity based on the additional markers selects compounds except the essence and the tobacco shreds as the additional markers, represents the uniformity of the perfuming process, can objectively and scientifically evaluate the uniformity of the cigarette perfuming process, and has unique advantages in the research of the cigarette perfuming uniformity.
(2) According to the current situation that the cigarette perfuming uniformity is not evaluated by using an external marker in related reports at present, the mandelic acid ester compound is selected as the external marker, the mandelic acid ester compound does not exist in cigarette essence or tobacco shreds or is not introduced in the production process, the mandelic acid ester compound is stable in physical and chemical properties, easy to extract and carry out qualitative and quantitative analysis, and the structure and the property of the mandelic acid ester compound are similar to various characteristic perfuming components in the cigarette essence and do not influence the fragrance style of the cigarettes, so that the uniformity of the cigarette perfuming process can be accurately and quantitatively evaluated, and the method has very important significance for evaluating the cigarette making process and stabilizing the product quality.
(3) The invention provides a method for detecting cigarette flavoring uniformity based on an additional marker, which is characterized in that a multi-reaction monitoring mode (MRM) detection method of gas chromatography tandem mass spectrometry (GC-MS/MS) is established for a standard product of a series of additional markers which are similar to the essence components in properties, are not added in various essences and do not exist in tobacco background. Accurately adding the product into essence, adding into tobacco shreds in flavoring process, performing Accelerated Solvent Extraction (ASE), performing quantitative determination, and calculating and evaluating the uniformity of cigarette flavoring process. Has very important significance for the evaluation of the silk making process and the stabilization of the product quality. The method has the advantages of simple operation, time saving, good reproducibility, low detection limit and strong practicability.
(4) The detection method for cigarette perfuming uniformity based on the additional marker provided by the invention adopts GC-MS/MS detection and analysis, and the obtained MRM spectrogram has the advantages of stable baseline, good separation degree, strong selectivity, high sensitivity and the like, and the quantitative detection result is more accurate.
(5) The method for detecting the cigarette perfuming uniformity based on the additional marker, provided by the invention, adopts an ASE pretreatment method, and is efficient, rapid and accurate in quantification.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The following examples used the following instruments and reagents:
1. reagent
A brand a essence sample, a brand a cigarette sample (supplied by tianjin cigarette factory); methanol (chromatographically pure, Merck, germany); isopropanol (chromatographically pure, Merck, germany); acetonitrile (chromatographically pure, Merck, germany); n-hexane (chromatographically pure, Merck, germany); dichloromethane (chromatographically pure, komeo); ethyl acetate (chromatographically pure, komel); benzoic acid phenethyl ester (95%, TCI); phenylethyl acetate (analytical grade, komel); phenylethyl propionate (98%, J & K); phenethylbutyrate (98%, Macklin); phenethyl phenylacetate (98%, J & K); benzyl acetate (98%, TCI).
2. Instrument for measuring the position of a moving object
7890A-7000B GC-tandem mass spectrometer (Agilent, USA); dionex ASE 350 accelerated solvent extractor (Thermo Fisher, USA); Milli-Q ultra pure water instruments (Millipore, USA); an XS204 electronic balance (0.0001g, Mettler, Switzerland); organic phase filtration membrane (nylon, 0.45 μm, Shanghai' an spectrum).
In one embodiment, the method for detecting the perfuming uniformity of the cigarette based on the added marker comprises the following detection process.
MS1 Scan pattern, Scan range 35-450a.m.u., for each fraction, characterized by NIST library search, confirmed retention time for each marker, and selected the most abundant ion for each marker as the parent ion. And then, determining the time segment and the residence time of each additional marker according to the obtained full-scan spectrogram, observing the ion scan diagram of each component parent ion, and selecting the characteristic daughter ion with the highest abundance as the daughter ion of the MRM method. And forming ion pairs by the determined parent ions and the determined daughter ions, respectively setting running sequences of different collision cell voltages, optimizing the optimal collision energy of each daughter ion, and finally using the optimized collision energy, wherein the ion source parameters are kept unchanged.
According to the principle of choice of the added marker: a) the added marker is not present in cigarette essence or tobacco shreds and can not be introduced in the production process. b) The added marker has stable physicochemical property, and is easy to extract and perform qualitative and quantitative analysis. c) The structure and the property of the added marker are similar to various characteristic aroma components in the cigarette essence, and the cigarette aroma style is not influenced.
The ester compounds in the tobacco essence are more in variety and play a key role in the quality of aroma, while the mandelate compounds are uniform in boiling point distribution, similar to the various ester compounds in the essence in chemical structure and property, are not added in the various essences and do not exist in the tobacco background, and are suitable to be used as an additional marker for evaluating the flavoring uniformity.
The phenethyl alcohol acid ester compound is selected from one or more of ethyl benzoate, ethyl phenylacetate, ethyl phenylpropionate, ethyl phenylbutyrate and ethyl phenylacetate.
The mandelic acid ester compound is used as an external marker and accurately added into the essence for cigarettes according to a certain proportion, the mixture is uniformly mixed to be used as the essence for the cigarettes, and the adding concentration of a single mandelic acid ester compound is 300-500 mg/mL. The parameters of the flavoring equipment are consistent with those adopted in normal production, and when the cut tobacco passes through the flavoring roller, the essence containing the added marker is sprayed into the cut tobacco to complete the cigarette flavoring process. After the perfuming equipment runs stably, tobacco shred samples of different batches are extracted at intervals of 0.9-1.1min and the like from the outlet of the perfuming roller at a fixed position, and the sampling amount of the tobacco shreds of different batches is 90-110 g/time.
Balancing the obtained tobacco shred sample at 20 + -2 deg.C and 60 + -5% relative humidity for 22-26 h. Grinding the balanced tobacco shred sample into fine powder, sieving, and sieving with a sieve with mesh size of 38-42 meshes. Grinding and uniformly mixing the screened tobacco shred sample and diatomite, adding an internal standard solution, and performing Accelerated Solvent Extraction (ASE). The mass ratio of the tobacco shred sample to the diatomite is 3.9-4.1: 1. The internal standard solution is an aqueous solution of benzyl acetate. The mass ratio of the benzyl acetate to the cigarette sample in the benzyl acetate aqueous solution is 0.9-1.1: 400000.
The processing conditions for accelerating the solvent extraction are as follows: the extraction solvent is selected from one of methanol, isopropanol, acetonitrile, n-hexane, dichloromethane or ethyl acetate; the extraction temperature is as follows: 60-140 ℃; static extraction time: 3-25 min; cycle number: 1-3 times; extraction pressure: 10-10.5 MPa; heating time: 3-7 min; leaching volume: 55-65 percent; nitrogen purging time: 45-75 s.
After the extraction of the accelerated solvent, filtering the extract by adopting a 0.45 mu m filter membrane, and analyzing by using a gas chromatography-tandem mass spectrometry (GC-MS/MS) to obtain the content of the external marker in the extract.
The measurement conditions of the gas chromatography were: a chromatographic column: HP-5MS capillary column (30 m.times.0.25 mm.times.0.25 μm); sample inlet temperature: 280 ℃ and 300 ℃; sample introduction amount: 0.5-2.0 μ L; carrier gas: high-purity helium, wherein the purity of carrier gas is more than or equal to 99.999 percent; flow rate of carrier gas: 0.5-1.5 ml/min; the split ratio is as follows: 10: 1; temperature rising procedure: the initial temperature was maintained at 60 ℃ for 2min and increased to 280 ℃ at a rate of 5 ℃/min for 10 min.
The mass spectrum measurement conditions were: an ionization mode: an Electron Impact (EI) ion source; ionization energy: 70 eV; ion source temperature: 250 ℃ and 270 ℃; quadrupole temperature: 140 ℃ and 160 ℃; transmission line temperature: 270 ℃ and 290 ℃; the scanning mode is as follows: MS1 Scan Scan, Product ion Scan, MRM Scan; and (3) data acquisition mode: MRM; and (3) spectrogram retrieval: NIST spectral library.
In the determination process, a standard substance of the mandelic ester compound is taken, added with ethanol for gradual dilution, and then added with an internal standard solution to prepare a series of standard working solutions with different concentrations. The standard working solution is obtained by adding ethanol into a standard substance of the phenethyl alcohol ester compound to dilute the standard substance step by step to obtain a mixed stock solution, adding an internal standard solution, and adding ethanol to dissolve and fix the volume. The mixed stock solution comprises a primary mixed stock solution and a secondary mixed stock solution, wherein the concentration of each mandelic ester compound in the primary mixed stock solution is 10000 mug/mL, and the concentration of each mandelic ester compound in the secondary mixed stock solution is 100 mug/mL. The concentration of each mandelate compound in the standard working solution is 0.10-10.00. mu.g/mL. The internal standard solution is an aqueous solution of benzyl acetate, the ratio of the added mass of the benzyl acetate in the internal standard solution to the added mass of the mandelic acid ester compound is 50: 5-500.
And respectively carrying out GC-MS/MS analysis on a series of standard working solutions with different concentrations to obtain a linear relation between the chromatographic peak area ratio of various mandelate compounds/internal standards and the concentration ratio of corresponding mandelate compounds/internal standards, drawing corresponding standard working curves, and calculating to obtain a regression equation of the standard working curves of various mandelate compounds. And performing GC-MS/MS analysis on the extract, substituting the obtained chromatographic peak area ratio of various mandelic ester compounds and the internal standard into a regression equation of a standard working curve of the corresponding mandelic ester compounds, and calculating the content of the corresponding mandelic ester compounds in the sample solution according to the known concentration of the internal standard.
Calculating the perfuming uniformity of the cigarettes according to formulas (1) and (2) by the content of corresponding mandelic acid ester compounds in the sample solution, wherein the formula (1) is used for calculating the standard deviation of the content of the additional markers in the perfumed cigarette samples of different batches, the formula (2) is used for calculating the variation coefficient of the content of the additional markers in the perfumed cigarette samples of different batches,
the formula (1) is:
the formula (2) is:
in the formula: SDiIs the standard deviation of the i-th applied marker content;
Sirthe amount of the ith additional marker in the sample of the batch r;
n is the batch of samples;
CVithe coefficient of variation of the i-th additional marker content.
The standard deviation SDiValue and coefficient of variation CViThe value comprehensively reflects the uniformity degree of the added markers with different boiling points in the cigarette flavoring process, SDiValue and CViThe smaller the value, the better the uniformity.
Example 1
According to the principle of choice of the added marker: a) the added marker is not present in cigarette essence or tobacco shreds and can not be introduced in the production process. b) The added marker has stable physicochemical property, and is easy to extract and perform qualitative and quantitative analysis. c) The structure and the property of the added marker are similar to various characteristic aroma components in the cigarette essence, and the cigarette aroma style is not influenced.
The ester compounds in the tobacco essence are more in variety and play a key role in the quality of aroma, while the mandelate compounds are uniform in boiling point distribution, similar to the various ester compounds in the essence in chemical structure and property, are not added in the various essences and do not exist in the tobacco background, and are suitable to be used as an additional marker for evaluating the flavoring uniformity.
The phenethyl alcohol acid ester compound comprises ethyl benzoate, ethyl phenylacetate, ethyl phenylpropionate, ethyl phenylbutyrate and ethyl phenylacetate.
The mandelic acid ester compound is used as an external marker and accurately added into the A-brand essence sample according to a certain proportion, the mixture is uniformly mixed and used as the essence for standby in the cigarette flavoring link, and the adding concentration of a single mandelic acid ester compound is 400 mg/mL. The parameters of the flavoring equipment are consistent with those adopted in normal production, and when the cut tobacco of the A-brand cigarette sample passes through the flavoring roller, the essence containing the additional marker is sprayed into the cut tobacco to finish the cigarette flavoring process. After the perfuming equipment runs stably, tobacco shred samples of different batches are extracted at intervals of 1.0min and the like from the outlet of the perfuming roller at a fixed position, and the sampling amount of the tobacco shreds of different batches is 100 g/time.
The obtained tobacco shred samples are balanced for 24 hours at the balance temperature of 20 +/-1 ℃ and the relative humidity of 60 +/-3%. Grinding the balanced tobacco shred sample into fine powder, sieving, and sieving with a 40-mesh sieve. Grinding and uniformly mixing the screened tobacco shred sample and diatomite, adding an internal standard solution, and performing Accelerated Solvent Extraction (ASE). The mass ratio of the added tobacco shred sample to the added diatomite is 4:1, namely 4.0g of tobacco shred sample and 1.0g (accurate to 0.0001g) of diatomite are ground and mixed uniformly. The internal standard solution is an aqueous solution of benzyl acetate. The mass ratio of the benzyl acetate to the tobacco shred samples in the benzyl acetate aqueous solution was 1:400000, namely, 0.1mL of 100. mu.g/mL benzyl acetate aqueous solution was added.
The processing conditions for accelerating the solvent extraction are as follows: extracting solvent: n-hexane; the extraction temperature is as follows: 100 ℃; static extraction time: 5 min; cycle number: 2 times; extraction pressure: 10.34 MPa; heating time: 5 min; leaching volume: 60 percent; nitrogen purging time: for 60 s.
After the extraction of the accelerated solvent, filtering the extract by adopting a 0.45 mu m filter membrane, and analyzing by using a gas chromatography-tandem mass spectrometry (GC-MS/MS) to obtain the content of the external marker in the extract.
The measurement conditions of the gas chromatography were: a chromatographic column: HP-5MS capillary column (30 m.times.0.25 mm.times.0.25 μm); sample inlet temperature: 290 ℃; sample introduction amount: 1.0 μ L; carrier gas: high-purity helium, wherein the purity of carrier gas is more than or equal to 99.999 percent; flow rate of carrier gas: 1.0 ml/min; the split ratio is as follows: 10: 1; temperature rising procedure: the initial temperature was maintained at 60 ℃ for 2min and increased to 280 ℃ at a rate of 5 ℃/min for 10 min.
The mass spectrum measurement conditions were: an ionization mode: an Electron Impact (EI) ion source; ionization energy: 70 eV; ion source temperature: 260 ℃; quadrupole temperature: 150 ℃; transmission line temperature: 280 ℃; the scanning mode is as follows: MS1 Scan Scan, Product ion Scan, MRM Scan; and (3) data acquisition mode: MRM; and (3) spectrogram retrieval: NIST spectral library.
In the determination process, a standard substance of the mandelic ester compound is taken, added with ethanol for gradual dilution, and then added with an internal standard solution to prepare a series of standard working solutions with different concentrations. The standard working solution is obtained by adding ethanol into a standard substance of the phenethyl alcohol ester compound to dilute the standard substance step by step to obtain a mixed stock solution, adding an internal standard solution, and adding ethanol to dissolve and fix the volume. The mixed stock solution comprises a primary mixed stock solution and a secondary mixed stock solution, wherein the concentration of each mandelic ester compound in the primary mixed stock solution is 10000 mug/mL, and the concentration of each mandelic ester compound in the secondary mixed stock solution is 100 mug/mL. The concentration of each mandelate compound in the standard working solution is 0.10-10.00. mu.g/mL. The internal standard solution is an aqueous solution of benzyl acetate, the ratio of the added mass of the benzyl acetate in the internal standard solution to the added mass of the mandelic acid ester compound is 50: 5-500.
And respectively carrying out GC-MS/MS analysis on a series of standard working solutions with different concentrations to obtain a linear relation between the chromatographic peak area ratio of various mandelate compounds/internal standards and the concentration ratio of corresponding mandelate compounds/internal standards, drawing corresponding standard working curves, and calculating to obtain a regression equation of the standard working curves of various mandelate compounds. And performing GC-MS/MS analysis on the extract, substituting the obtained chromatographic peak area ratio of various mandelic ester compounds and the internal standard into a regression equation of a standard working curve of the corresponding mandelic ester compounds, and calculating the content of the corresponding mandelic ester compounds in the sample solution according to the known concentration of the internal standard.
Example 2
In the determination process, 0.5000g (accurate to 0.0001g) of each of 5 kinds of phenylethanolate standard substances is accurately weighed and placed in a 50mL volumetric flask, dissolved by ethanol and subjected to constant volume to obtain a primary mixed standard stock solution with the mass concentration of 10000 mug/mL, then 0.5mL of the primary stock solution is subjected to constant volume to the 50mL volumetric flask to obtain a secondary mixed standard stock solution with the mass concentration of 100 mug/mL, and the secondary mixed standard stock solution is stored in a refrigerator at 4 ℃. Accurately transferring 0.05 mL, 0.25 mL, 0.50 mL, 2.50 mL and 5.00mL of secondary mixed standard stock solutions into a 50mL volumetric flask, respectively adding 0.5mL of benzyl acetate internal standard solution (100 mu g/mL), and performing constant volume with ethanol to obtain series of standard working solutions with the concentrations of 0.10, 0.50, 1.00, 5.00 and 10.00 mu g/mL respectively.
Performing GC-MS/MS analysis on a series of standard working solutions with different concentrations respectively to obtain a linear relation between the chromatographic peak area ratio of various mandelate compounds/internal standards and the concentration ratio of the corresponding mandelate compounds/internal standards, drawing corresponding standard working curves, and calculating to obtain regression equations of the standard working curves of various mandelate compounds, wherein the results are shown in Table 1. As can be seen from Table 1, the peak areas of 5 mandelates at concentrations of 0.1-10. mu.g/mL showed good linear relationship and correlation coefficient (R)2) Are all above 0.99. The detection limit of the compound is determined to be 0.01 mu g/mL by 3 times of signal-to-noise ratio respectively, and the sensitivity is higher.
Table 15 linear regression equations, correlation coefficients and detection limits for mandelate
Example 3
According to the perfuming and sampling method in the example 1, the same batch of flavored cut tobacco samples are selected, 5 parts are weighed in parallel, the low, medium and high three concentration levels of the phenylethanolate standard solution are respectively and quantitatively added, and the recovery rate of each phenylethanolate is calculated according to the content average value measured before and after the addition of the standard. The recovery rate of 5 kinds of phenylglycolate under each addition level is 90.98-107.17%, which shows that the recovery rate of the method is better. The Relative Standard Deviation (RSD) of the 5 mandelates was below 10%, indicating that the reproducibility of the process was good and the results are shown in Table 2.
Table 2 recovery and reproducibility evaluation of 5 mandelates at different addition levels (n ═ 5)
Example 4
Selecting 10 batches of cut tobacco samples with a certain brand according to the flavoring and sampling method in the example 1, determining the cut tobacco samples by adopting the GC-MS/MS condition in the example 1, calculating the flavoring uniformity of the cigarettes according to the formulas (1) and (2) according to the content of corresponding phenylglycolate compounds in a sample solution, wherein the formula (1) is used for calculating the standard deviation of the content of the additional markers in the flavored cigarette samples of different batches, the formula (2) is used for calculating the variation coefficient of the content of the additional markers in the flavored cigarette samples of different batches, and the specific result is shown in a table 3,
the formula (1) is:
the formula (2) is:
in the formula: SDiIs the standard deviation of the i-th applied marker content;
Sirthe amount of the ith additional marker in the sample of the batch r;
n is the batch of samples;
CVithe coefficient of variation of the i-th additional marker content.
TABLE 3 perfuming uniformity evaluation of 5 mandelates in different batches of tobacco shreds
Due to standard deviation SDiValue and coefficient of variation CViThe value comprehensively reflects the uniformity of the added markers with different boiling points in the cigarette flavoring process, and the SD of the mandelate with different boiling points can be seen from Table 1iValue and CViThe values are all small, and the perfuming link has better uniformity.
Example 5
A certain grade of cut tobacco sample of the same batch is selected, methanol, isopropanol, acetonitrile, normal hexane, dichloromethane and ethyl acetate are respectively adopted as extraction solvents, and measurement is carried out according to the perfuming and sampling methods in the example 1 and the GC-MS/MS conditions in the example 1. According to the extraction efficiency of different solvents to the target object and the number and content of extracted impurities, n-hexane can be obtained as the extraction solvent, the extraction efficiency is high, and the matrix interference is minimum.
The same batch of cut tobacco samples with a certain grade are selected, the extraction effects of 60 ℃, 80 ℃, 100, 120 and 140 ℃ are respectively considered, and when the extraction temperature is 60 ℃ and 80 ℃, the recovery rates of the ethyl benzoate are lower and are respectively 78.13 percent and 81.30 percent. When the extraction temperature is 100 ℃, the recovery rate of the 5 kinds of the phenylglycolic acid ester reaches 95.48 to 100.97 percent. There was no significant difference in recovery as the temperature continued to rise to 120 ℃. When the extraction temperature is raised to 140 ℃, the recovery rate is reduced to 88.57-96.91%. The dissolving capacity of the analyzed substance can be improved by increasing the extraction temperature, the acting force between the solvent and the sample matrix is reduced, and the extraction efficiency is improved; however, too high a temperature may cause degradation of the target substance and increase in the solvent density, decrease the diffusion coefficient, and decrease the recovery rate. And considering that the higher the temperature, the more energy is consumed, the extraction temperature is the best at 100 ℃.
Selecting a certain grade of cut tobacco samples in the same batch, setting the static extraction time to be 5min, 10min, 15 min, 20 min and 25min respectively, and inspecting the influence on the extraction result. The diffusion of the extract to the extraction reagent can be increased by increasing the static extraction time, so that the extraction rate is improved; however, the static extraction time at high temperature increases the possibility of thermal degradation of the extract, reducing the recovery. The result of the recovery rate after adding the standard shows that the recovery rate reaches 96.19-103.51% in 5min, and the recovery rate has no obvious difference along with the extension of the extraction time, thereby meeting the analysis requirement. For shortening the analysis time, the static extraction time is preferably 5 min.
Selecting a certain grade of cut tobacco sample in the same batch, and investigating the influence of the cycle times of the static extraction time on the extraction, wherein the cycle times are respectively 1,2 and 3. Because the static extraction time is divided into different cycles, rather than simply lengthening the time of a single extraction, fresh solvent can be introduced in the middle of the extraction, which helps to maintain an effective solvent/sample balance, especially for high concentration samples or difficult to extract samples. The recovery rate of the cycle 2 is obviously improved to 1, and reaches 95.26-105.42%, while the recovery rate of the cycle 3 is not obviously increased compared with the recovery rate of the cycle 2. In order to reduce the amount of organic solvent used, the number of cycles is preferably 2.
Example 6
When 5 types of mandelate and internal standard solution are subjected to GC-MS/MS analysis, performing MS1 Scan mode full Scan on the standard working solution, wherein the Scan range is 35-450a.m.u., the retention time of each marker is confirmed by NIST spectral library retrieval, and ions with the highest abundance of each marker are selected as parent ions; determining time segments and residence time of each additional marker by a full-scan spectrogram, observing a scanning picture of the daughter ions of each component parent ion, and selecting the characteristic daughter ion with the highest abundance as the daughter ion of the MRM method; the method comprises the steps that parent ions and child ions form ion pairs, running sequences of different collision cell voltages are set respectively, the optimal collision energy of each child ion is optimized, the optimized collision energy is used finally, and ion source parameters are kept unchanged.
The MRM scan parameters for the 5 mandelate and internal standard solutions are shown in table 4.
Table 45 MRM scan parameters of mandelate and internal standards
*Quantitative ion
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. A method for detecting cigarette perfuming uniformity based on an additional marker comprises the following steps: adding a phenylglycollate compound serving as an external marker into tobacco essence, adding the tobacco essence containing the external marker into tobacco shreds through a flavoring process, balancing, grinding and screening the flavored tobacco shreds in different batches, extracting with an accelerating solvent to obtain extraction liquid of the tobacco shreds in different batches respectively, performing gas chromatography tandem mass spectrometry analysis on the extraction liquid to obtain the content of the external marker in a plurality of extraction liquids, and further calculating to obtain the flavoring uniformity of the cigarettes;
the phenethyl alcohol acid ester compound is selected from one or more of ethyl benzoate, ethyl phenylacetate, ethyl phenylpropionate, ethyl phenylbutyrate and ethyl phenylacetate;
the processing conditions for accelerating the solvent extraction are as follows: the extraction solvent is selected from one of methanol, isopropanol, acetonitrile, n-hexane, dichloromethane or ethyl acetate; the extraction temperature is as follows: 60-140 ℃; static extraction time: 3-25 min; cycle number: 1-3 times; extraction pressure: 10-10.5 MPa; heating time: 3-7 min; leaching volume: 55-65 percent; nitrogen purging time: 45-75 s;
adding an internal standard solution during the accelerated solvent extraction, wherein the internal standard solution is an aqueous solution of benzyl acetate;
in the gas chromatography tandem mass spectrometry, the determination conditions of the gas chromatography are as follows:
a chromatographic column: HP-5MS capillary column, 30m × 0.25mm × 0.25 μm; sample inlet temperature: 280 ℃ and 300 ℃; sample introduction amount: 0.5-2.0 μ L; carrier gas: high-purity helium, wherein the purity of carrier gas is more than or equal to 99.999 percent; flow rate of carrier gas: 0.5-1.5 ml/min; the split ratio is as follows: 10: 1; temperature rising procedure: the initial temperature was maintained at 60 ℃ for 2min and increased to 280 ℃ at a rate of 5 ℃/min for 10 min.
2. The method for detecting the perfuming uniformity of the cigarette based on the external marker as claimed in claim 1, wherein the adding concentration of the individual mandelate compounds is 300-500 mg/mL.
3. The method for detecting the cigarette perfuming uniformity based on the additional marker according to claim 1, wherein the sampling interval time of the tobacco shreds of different batches is 0.9-1.1 min; the sampling amount of the cut tobacco of different batches is 90-110 g/time.
4. The method for detecting the cigarette perfuming uniformity based on the additional marker as claimed in claim 1, wherein the accelerated solvent extraction further comprises any one or more of the following conditions:
A1) before the accelerated solvent extraction, grinding and uniformly mixing the sieved tobacco shred sample with diatomite; the mass ratio of the tobacco shred sample to the diatomite is 3.9-4.1: 1;
A2) the mass ratio of the benzyl acetate to the tobacco shred samples in the benzyl acetate aqueous solution is 0.9-1.1: 400000.
5. The method for detecting cigarette perfuming uniformity based on external markers, according to claim 1, wherein in the gas chromatography tandem mass spectrometry, the mass spectrometry determination conditions are as follows:
an ionization mode: electron bombardment of an EI ion source; ionization energy: 70 eV; ion source temperature: 250 ℃ and 270 ℃; quadrupole temperature: 140 ℃ and 160 ℃; transmission line temperature: 270 ℃ and 290 ℃; the scanning mode is as follows: MS1 Scan Scan, Product ion Scan, MRM Scan; and (3) data acquisition mode: MRM; and (3) spectrogram retrieval: NIST spectral library.
6. The method for detecting the cigarette perfuming uniformity based on the additional marker as claimed in claim 1, wherein the additional marker is quantified by an internal standard curve method, and the internal standard curve method comprises the following steps:
A) taking a standard substance of a mandelate compound, adding ethanol for gradual dilution, and then adding an internal standard solution to prepare a series of standard working solutions with different concentrations;
B) respectively carrying out GC-MS/MS analysis on a series of standard working solutions with different concentrations in the step A) to obtain a linear relation between the chromatographic peak area ratio of various mandelate compounds/internal standards and the concentration ratio of the corresponding mandelate compounds/internal standards, drawing corresponding standard working curves, and calculating to obtain regression equations of the standard working curves of the various mandelate compounds;
C) and C, performing GC-MS/MS analysis on the extract, substituting the obtained chromatographic peak area ratio of various mandelic ester compounds and the internal standard into a regression equation of the standard working curve of the corresponding mandelic ester compound in the step B), and calculating the content of the corresponding mandelic ester compound in the sample solution according to the known concentration of the internal standard.
7. The method for detecting the cigarette flavoring uniformity based on the additional marker according to claim 1, wherein the cigarette flavoring uniformity is calculated according to the formulas (1) and (2), the formula (1) is used for calculating the standard deviation of the content of the additional marker in the flavored cigarette samples of different batches, the formula (2) is used for calculating the variation coefficient of the content of the additional marker in the flavored cigarette samples of different batches,
the formula (1) is:
the formula (2) is:
in the formula: SDiIs the standard deviation of the i-th applied marker content;
Sirthe amount of the ith additional marker in the sample of the batch r;
n is the batch of samples;
CVithe coefficient of variation of the i-th additional marker content.
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| CN111426716B (en) * | 2020-05-15 | 2023-03-31 | 云南中烟工业有限责任公司 | Cut tobacco perfuming uniformity detection method based on XPS |
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| CN111707745A (en) * | 2020-06-12 | 2020-09-25 | 上海烟草集团有限责任公司 | A method for evaluating the uniformity of cigarette flavoring |
| CN114088583B (en) * | 2021-11-01 | 2024-03-19 | 河南中烟工业有限责任公司 | A method for establishing a diffusion model of liquid applied in heated cigarettes |
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