CN107941978B - Method for evaluating internal quality stability of bead blasting for cigarettes - Google Patents
Method for evaluating internal quality stability of bead blasting for cigarettes Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention relates to a method for evaluating the internal quality stability of cigarette blasting beads, which comprises the steps of grinding a plurality of batches of cigarette blasting bead samples respectively, filtering to obtain blasting bead inclusions, adding an internal standard solution into the blasting bead inclusions, extracting, taking supernatant, filtering to obtain filtrate, wherein the ratio of the blasting bead inclusions to the internal standard in the internal standard solution is 1m L (0.5-2.0) mg, carrying out gas chromatography-mass spectrometry combined analysis on the filtrate, determining a common peak by taking an internal standard peak as a reference peak, calculating the relative retention time α and the relative peak area S value of a chromatographic peak in the cigarette blasting bead samples, establishing a chromatographic fingerprint of each blasting bead inclusion sample, and respectively calculating the Euclidean distance, the Euclidean distance ratio and the similarity by using the relative peak area S value of each component of each batch of cigarette blasting bead samples to evaluate the internal quality stability of the cigarette blasting beads.
Description
Technical Field
The invention belongs to the technical field of tobacco materials, and particularly relates to a method for evaluating the internal quality stability of a bead blasting for tobacco.
Background
The bead blasting technology for cigarettes is characterized in that one or more flavor capsules which are easy to break are implanted in the production process of a filter tip, so that the characteristic flavor release which is artificially controllable in the smoking process of the cigarettes is realized, and the influence of the external environment on the smoking flavor and the loss of flavor caused by the external environment are reduced. The bead blasting for cigarettes has an important role in improving the taste of cigarettes, compensating and enhancing the fragrance of the cigarettes and highlighting the style of the cigarettes, and more cigarette production enterprises are dedicated to the research and development of the bead blasting cigarettes.
At present, the research on the bead blasting for the cigarettes mainly comprises the development and preparation of the inclusion of a novel bead blasting for the cigarettes, the influence of the bead blasting for the cigarettes on the release amount of harmful components in main stream smoke and the interception of a filter tip and the like, and the evaluation on the quality stability of the bead blasting for the cigarettes is only limited to the evaluation on physical indexes such as bead blasting diameter, rubber thickness, crushing pressure and appearance. At present, no method for evaluating the inherent quality stability of the bead blasting for cigarettes is reported. The cigarette bead blasting inclusion is prepared by blending various spices and a proper amount of solvent, is influenced by various factors such as a raw material producing area, a processing technology and the like, has certain fluctuation in product quality, cannot essentially reflect the components of the cigarette bead blasting inclusion only through physical indexes and sensory judgment, and is difficult to accurately and objectively grasp the quality change of the cigarette bead blasting inclusion. Therefore, it is necessary to establish a method for evaluating the quality stability of the bead blasting for cigarettes. The content of the bead blasting for the cigarette is complex, and if only individual chemical indexes are analyzed, the change of the internal quality of the bead blasting for the cigarette is difficult to effectively monitor.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a method for evaluating the internal quality stability of a cigarette bead, which can effectively monitor the internal quality change of the cigarette bead.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method comprises the following steps:
the method comprises the following steps:
(1) respectively grinding a plurality of batches of bead blasting samples for cigarettes, then, passing through a membrane to obtain bead blasting inclusions, adding an internal standard solution into the bead blasting inclusions, extracting, and then, taking supernatant to pass through the membrane, wherein the ratio of the bead blasting inclusions to the internal standard in the internal standard solution is 1m L (0.5-2.0) mg;
(2) analyzing the supernatant after the membrane is passed by adopting a gas chromatography-mass spectrometry combined method, determining a common peak by taking an internal standard peak as a reference peak, solving the relative retention time α and the relative peak area S value of a chromatographic peak in a cigarette bead blasting sample, and establishing a chromatographic fingerprint of each bead blasting content sample;
(3) and respectively solving the Euclidean distance, the Euclidean distance ratio and the similarity by using the relative peak area S value of each component of each batch of the cigarette bead blasting samples, and evaluating the inherent quality stability of the cigarette bead blasting.
Further, the membrane-filtered after the grinding in the step (1) is a membrane-filtered by a 0.22 μm or 0.45 μm organic phase syringe.
Further, the internal standard solution in the step (1) is a n-hexane solution of n-heptadecane.
Further, oscillation extraction is adopted in the extraction in the step (1), and the extraction time is 20-60 min.
Further, the conditions in the gas chromatography-mass spectrometry combined analysis in the step (2) are that a chromatographic column is an Agilent HP-5MS capillary column with the specification of 30m × 0.32mm × 0.25.25 μm, the split ratio is (5-30): 1, the sample injection amount is 1 μ L, the temperature is programmed to be 60-80 ℃ at the initial temperature and kept for 3min, then the temperature is increased to 160 ℃ at the heating rate of 5 ℃/min and then increased to 280 ℃ at the heating rate of 10 ℃/min and kept for 10min, carrier gas is helium, the carrier gas flow rate is 0.8-1.2 m L/min, the sample injection port temperature is 280 ℃, the transmission line temperature is 280 ℃, the solvent delay is 3.5min, the ionization mode is EI, the ionization energy is 70eV, the temperature is 230 ℃, the quadrupole ion source temperature is 150 ℃, the scanning mode is a Scan mode, and the scanning range is 35-500 amu.
Further, in the analysis of the gas chromatography-mass spectrometry combination method, a NIST library is adopted for retrieval and qualitative determination, and an internal standard relative peak area method is adopted for quantification.
Further, in the step (2), the calculation formula of the relative retention time α and the relative peak area S value is:
α＝tr/tis(1)
S＝Sr/Sis(2)
wherein, trIs the retention time of the peak to be measured; t is tisIs the retention time of the internal standard; s is the relative peak area; srIs the peak area of each sample component; sisIs the peak area of the internal standard.
Further, assuming that the number k of characteristic peaks is 1, 2, …, m, in step (3), the calculation formula of euclidean distance, euclidean distance ratio and similarity is:
similarity is equal to Euclidean distance ratio × included angle cosine value (6)
Wherein d is the Euclidean distance; xkIs S of the kth peak of sample Xr；XrIs the kth peak S of the batch samplerThe mean value of (a); c is the cosine of the included angle; y iskIs S of the kth peak of sample Yr。
Further, in the step (3), performing cluster analysis on the chromatographic fingerprint of each sample of the content of the cigarette popping beads, measuring by using an Euclidean distance, connecting every two samples by using an inter-class average chain method, outputting a system cluster analysis dendrogram, taking the abscissa of the system cluster analysis dendrogram as a critical value, and judging the quality stability of different batches of samples of the cigarette popping beads according to the size of the critical value.
Further, in the step (1), diluting and blending essence and spice respectively for the explosive bead contents, then respectively adding internal standard solution, extracting, taking the supernatant fluid to pass through a membrane, and carrying out gas chromatography-mass spectrometry combined analysis to obtain the chromatographic fingerprint of the diluted sample and the chromatographic fingerprint of the blended sample; in the step (3), the chromatographic fingerprint of each explosive inclusion sample, the chromatographic fingerprint of the diluted sample and the chromatographic fingerprint of the blended sample are subjected to cluster analysis.
Compared with the prior art, the invention has the following beneficial technical effects:
the chromatographic fingerprint spectrum utilized in the invention is a method for integrally researching a complex chemical composition system, has the characteristics of fingerprint characteristic analysis, macroscopic inference analysis and the like, and is suitable for investigating the uniformity and stability of the internal quality of complex compositions. The method can comprehensively analyze the internal quality of the cigarette blasting beads and reflect the fluctuation condition of the internal quality, provides a quick, simple, convenient and reliable method for controlling the internal quality of the cigarette blasting beads, and is favorable for improving the safety control level of the quality of the cigarette blasting beads in the cigarette industry.
Further, aiming at the problems that the quality evaluation of the existing bead blasting for cigarettes is only limited to the evaluation of physical indexes, the internal quality condition of the bead blasting for cigarettes cannot be comprehensively reflected, the complex comparison process is avoided, the missing information is avoided and the like, the method combines the chromatographic fingerprint spectrum with the cluster analysis, and establishes the evaluation method suitable for the internal quality stability of the bead blasting for cigarettes. According to the invention, through a cluster analysis method, the most similar objects are combined together according to the affinity and sparseness between observed values or variables, and the observed values are classified in a successive aggregation mode until all samples are finally aggregated into one type. Therefore, the method for evaluating the internal quality stability of the cigarette blasting beads by combining the chromatographic fingerprint with the clustering analysis is applied to the evaluation research of the internal quality stability of the cigarette blasting beads, and can be established.
Drawings
FIG. 1 shows fingerprint spectra of different batches of the contents of a cigarette blasting bead A;
FIG. 2 is a clustering analysis dendrogram of a sample system for a cigarette blasting bead A.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The invention comprises the following steps:
(1) pretreatment of bead blasting sample for cigarette
Grinding a bead blasting sample, and filtering the bead blasting sample through a 0.22 mu m or 0.45 mu m organic phase needle head filter membrane to obtain a bead blasting inclusion for later use, accurately transferring 0.3-1.0 m L bead blasting inclusion into a 50m L triangular flask with a stopper by using a liquid transfer gun, adding 3.0-10.0 m L n-hexane solution containing an internal standard substance with a certain concentration, performing oscillation extraction for 20-60 min, standing, filtering a supernatant through an organic phase filter membrane, and performing gas chromatography-mass spectrometry analysis, wherein the volume ratio of the bead blasting inclusion to the internal standard solution is 1:10, the concentration range of the internal standard solution is 0.05-0.2 mg/m L, and therefore the ratio of the bead blasting inclusion to the internal standard substance in the internal standard solution is 1m L (0.5-2.0) mg.
(2) Gas chromatography-mass spectrometry combined analysis condition
The chromatographic column comprises an Agilent HP-5MS capillary column (specification: 30m × 0.32.32 mm × 0.25.25 μm), a split-flow ratio of 5-30: 1, a sample introduction amount of 1 μ L, a programmed temperature rise of 60-80 ℃, 3min, 160 ℃ at a temperature rise rate of 5 ℃/min, 280 ℃ at a temperature rise rate of 10 ℃/min, 10min at a temperature rise rate of 10 ℃/min, helium gas as a carrier gas, a carrier gas flow rate of 0.8-1.2 m L/min, a sample introduction port temperature of 280 ℃, a transmission line temperature of 280 ℃, solvent delay of 3.5min, an ionization mode of EI, ionization energy of 70eV, an ion source temperature of 230 ℃, a quadrupole rod temperature of 150 ℃, a scanning mode of Scan mode, a scanning range of 35-500 amu, a NIST spectral library is adopted for qualitative retrieval, and an internal standard is quantitative relative to a peak area method.
(3) Establishment of chromatographic fingerprint of content of popping beads for cigarettes in different batches
The method comprises the steps of measuring different batches of tobacco blasting bead content samples and diluted and blended samples by adopting a gas chromatography-mass spectrometry combined method, wherein a graph 1 shows chromatographic fingerprint spectrums of different batches of tobacco blasting bead A content samples, an internal standard peak is used as a reference peak, different batches of samples jointly contain a component chromatographic peak which is well separated and stable as a common peak, the relative retention time α and the relative peak area S of a main chromatographic peak (a peak which has better separation degree and larger peak area and can represent the component of the blasting bead content) in the samples are respectively calculated according to formulas (1) and (2), the chromatographic fingerprint spectrum of each blasting bead content sample is established, the relative peak area S of each component of each batch of blasting bead content samples is respectively substituted into Euclidean distance, the Euclidean distance ratio and an included angle cosine formula (formula 3-6), and the quality stability of each batch of the blasting bead content samples is evaluated by comparing the Euclidean distance, the Euclidean distance ratio, the similarity and the like.
α＝tr/tis(1)
S＝Sr/Sis(2)
Similarity is equal to Euclidean distance ratio × included angle cosine value (6)
Where α -relative retention time, tr-retention time of the peak to be measured; t is tis-retention time of internal standard; s-relative peak area; sr-peak area of each sample component; sis-peak area of internal standard; d is the Euclidean distance; xkS of the kth peak of sample Xr；XrKth peak S of batch samplerThe mean value of (a); c-cosine of the included angle; y iskS of the kth peak of sample Yr(ii) a Let the number k of characteristic peaks be 1, 2, …, m.
(4) Cluster analysis of bead blasting content for different batches of cigarettes
And (3) performing cluster analysis on the chromatographic data of each batch of bead blasting samples by adopting a system cluster analysis method in SPSS data statistical software, and visually judging the inherent quality stability of each batch of bead blasting samples according to a system cluster analysis dendrogram and a critical value between samples. SPSS software is adopted to carry out cluster analysis on chromatographic fingerprint data of different batches of cigarette bead blasting samples and diluted and blended samples thereof, Euclidean distance measurement is carried out, every two samples are connected by an inter-class average chain method, finally, a system cluster analysis dendrogram is output, and the critical value is the horizontal coordinate of the system cluster analysis dendrogram after the data are processed by the system cluster analysis method. According to the size of the critical value, the similarity degree of the two samples can be judged, and the smaller the critical value is, the more similar the samples are.
According to the method, the fingerprint spectrum of the contents of the cigarette blasting beads is obtained through a gas chromatography-mass spectrometry combined method, the chromatographic fingerprint spectrum and clustering analysis are combined, and the evaluation method suitable for the stability of the internal quality of the cigarette blasting beads is established.
The method is mainly characterized in that the macroscopic integrity of the chromatographic fingerprint is combined with the intuitiveness of the cluster analysis, so that the integral monitoring of the internal quality of the bead blasting for the cigarettes is realized.
The invention is further illustrated by the following specific examples.
Example 1
1. Material
1.1 materials, reagents and instruments
Three types of bead blasting samples for cigarettes with honey sweet flavor, fresh sweet flavor and mint flavor, which are produced by Guangzhou Xingye Biotechnology Limited, are respectively numbered A-C.
N-hexane is chromatographically pure.
7890B-5977A gas chromatography-mass spectrometry (Agilent, USA), HP-5MS capillary column (specification: 30m × 0.32mm × 0.25 μm, Agilent, USA), KQ-700DB numerical control ultrasonic extraction apparatus (ultrasonic apparatus, Inc., Kunshan city), HY-8 type oscillator (China electric apparatus, Inc., Changzhou) and 0.45 μm organic phase needle filter membrane (Jinteng).
2. Method of producing a composite material
2.1 treatment of the samples
Grinding a sample of the popping beads by using a mortar, taking the content of the popping beads, and filtering the content of the popping beads through a 0.45-micron organic phase needle filter membrane for later use, accurately transferring 0.5m L content of the popping beads into a 50m L triangular flask, adding 5.0m L n-hexane solution containing n-heptadecane, wherein the concentration of the n-hexane solution containing n-heptadecane is 0.05mg/m L, at the moment, the ratio of the content of the popping beads to the internal standard substance in the internal standard solution is 1m L: 0.5mg, oscillating and extracting for 30min, standing, taking the supernatant, filtering the supernatant through the organic phase filter membrane by using a mass spectrometry method, and carrying out gas chromatography analysis.
2.2 gas chromatography Mass Spectrometry analysis
The analysis conditions comprise a chromatographic column, an Agilent HP-5MS capillary column (specification: 30m × 0.32mm × 0.25 mu m), a split flow ratio of 10:1, a sample introduction amount of 1 mu L, a programmed temperature rise of 60 ℃, 3min, 160 ℃ at a temperature rise rate of 5 ℃/min, 280 ℃ at a temperature rise rate of 10 ℃/min, 10min at a sample introduction port, helium gas as a carrier gas, a carrier gas flow rate of 1.0m L/min, a transmission line temperature of 280 ℃, a solvent delay of 3.5min, an ionization mode of EI, 70eV of ionization energy, 230 ℃ of an ion source, 150 ℃ of a quadrupole rod, a scanning mode of Scan mode and a scanning range of 35-500 amu.
And (4) performing retrieval and qualitative by adopting an NIST spectral library, and quantifying by using an internal standard relative peak area method.
2.3 establishment of fingerprint spectrum of explosive bead inclusion for cigarette
The method comprises the steps of respectively measuring 5 batches of content samples and diluted and blended samples of three types of blasting beads A, B, C by adopting a gas chromatography-mass spectrometry combined method, taking a normal heptadecane internal standard peak as a reference peak, selecting 5 batches of component chromatographic peaks which jointly contain, are well separated and are stable as common peaks, keeping the retention time within 30min, respectively obtaining the relative retention time α and the relative peak area S value of a main chromatographic peak in the samples according to a formula, establishing a chromatographic fingerprint of each blasting bead content sample, respectively enabling the total peak area of the common peaks of the 5 batches of samples to respectively occupy more than 80% of the total peak area, and showing the characteristics of each batch of samples of the cigarette blasting beads.
Table 1 shows the S values of 5 batches of the blasting beads A and the diluted and blended samples, and it can be seen from Table 1 that 5 batches of the blasting beads A1-A51 of (1)The S values of the 5 common peaks are relatively close, the S value of each peak is gradually reduced as the dilution concentration of the blasting bead A sample is reduced, and the S value of each peak is gradually reduced as the doping concentration of the blasting bead A sample is increased.
TABLE 1 burst A5 lot samples and S values of diluted blended samples
Note: a, diluting the content concentration of the blasting bead A by using normal hexane; b, mixing the content of the blasting bead A with other essence and spice samples with the volume fraction of 10-40%. Pretreating the diluted sample and the blended sample by adding an n-hexane solution containing an internal standard substance with a certain concentration; the blended essence and spice sample can be a sweet type inclusion of the popsicle.
Common methods for calculating the similarity include an Euclidean distance method, an included angle cosine method, a correlation coefficient method and the like, and in view of the complexity of components of a sample containing the blasting beads, a single parameter is difficult to accurately reflect the similarity among the samples, and the similarity among the samples can be evaluated by adopting the product of the Euclidean distance ratio and the included angle cosine among different samples.
2.3.1 Euclidean distance
The Euclidean distance similarity can reflect the degree of affinity and sparseness among samples, the quality of the samples cannot be judged according to Euclidean distance data, but the change of the samples can be judged according to the multiple relation between batch samples and diluted and blended samples. The Euclidean distances of the explosive A-C content samples and the respective diluted samples and blended samples were calculated according to the formula (3) and are shown in Table 2. As can be seen from Table 2, the quality of the 5 batches of three types of shot samples is relatively stable, and the Euclidean distance value becomes significantly larger as the dilution and blending ratio increases. The Euclidean distance variation range of 5 batches of samples of the bead blasting A is 0.10-0.27, the Euclidean distance variation range of 5 batches of samples of the bead blasting B is 1.24-8.01, the Euclidean distance variation range of 5 batches of samples of the bead blasting C is 0.01-0.08, and the numerical values can be used as important indexes of quality stability of different batches of samples of the bead blasting A-C after investigation.
TABLE 2 Euclidean distances of exploding bead A-C content samples
2.3.2 fingerprint Euclidean distance ratio and similarity of the content of the blasting beads for cigarettes
According to the formula, the Euclidean distance ratio, the cosine of the included angle and the similarity are calculated for three different batches of the blasting beads and diluted and blended samples thereof, the results are shown in Table 3, A, B, C are respectively standard samples of the three blasting beads, A1、B1、C1The samples are different batches of the three kinds of blasting beads, the dilution concentrations of the three kinds of blasting beads are respectively 80%, 60%, 40% and 20%, the blending concentrations are 10%, 20%, 30% and 40%, and as can be seen from table 3, the Euclidean distance ratios and the similarity of the samples of different batches are all above 0.9, which indicates that the quality stability of the samples of different batches is good; with the increase of dilution and blending concentration, the Euclidean distance ratio and the similarity are gradually reduced, the cosine value of the included angle is not obviously changed, the contribution of the Euclidean distance ratio to the similarity is large, the change of the component concentration of a sample can be better reflected, and the Euclidean distance ratio can be used as an important index for quality stability investigation of the content of the blasting shots.
TABLE 3 Euclidean distance ratio, angle cosine and similarity of different batches of explosive inclusion samples and diluted blended samples
2.3.3 Cluster analysis of fingerprint of explosive inclusions
By comparing the data in table 1, diluted and blended samples can be distinguished, but the comparison process is complicated, partial information is easy to miss, and the comparison process is not intuitive enough, so that SPSS19.0 software is adopted to perform cluster analysis on the chromatographic fingerprint data of 5 batches of the cigarette blasting bead A sample and diluted (dilution concentration is 80%, 60%, 40% and 20%), blended (blending concentration is 10%, 20%, 30% and 40%) samples thereof. And measuring by using Euclidean distance, connecting every two samples by using an inter-class average chain method, and finally outputting a system clustering analysis dendrogram, wherein the abscissa is a critical value and the ordinate is a sample name as shown in figure 2. A smaller cutoff value indicates a more similar spectrum. When the critical value is about 1, 5 batches of samples of the cigarette blasting bead A are grouped into one, when the critical value is about 2, 80% of A dilution and 10% of A mixing are grouped into one, and when the critical value is between 2 and 6, 5 batches of samples of the cigarette blasting bead A can be divided into two types, namely 80% of A dilution and 10% of A mixing, and the samples can be successfully distinguished by a systematic clustering analysis method. It can also be seen from fig. 2 that the farther the diluted and spiked sample is from the batch sample, the less similar as the dilution and spiked concentration increases.
Comparative example 1
Phenethyl acetate is used as an internal standard instead of the n-heptadecane in example 1, and other conditions are the same as in example 1.
Tests show that the peak time of the phenethyl acetate is overlapped with the components in the sample, the retention time of the n-heptadecane is 24.701min, the chemical property is stable, the chromatographic peak shape is good, and the sample has no peak at the position, so the n-heptadecane is selected as the internal standard substance for the analysis of the explosive bead contents.
Example 2
1. Materials, reagents and apparatus were the same as in example 1.
2.1 treatment of the samples
Grinding a bead blasting sample by using a mortar, taking the contents of the bead blasting sample to be reserved after filtering the contents of the bead blasting sample by using a 0.22 mu m organic phase needle filter membrane, accurately transferring 0.3m L bead blasting contents into a 50m L triangular flask by using a liquid transfer gun, adding 3.0m L n-hexane solution containing n-heptadecane, oscillating and extracting for 20min, standing, taking the supernatant to pass through the organic phase filter membrane, and analyzing by using a gas chromatography-mass spectrometry combination method, wherein the concentration of the n-hexane solution containing the n-heptadecane is 0.12mg/m L, so that the ratio of the contents of the bead blasting sample to the internal standard substance in the internal standard solution is 1m L: 1.2 mg.
2.2 gas chromatography-Mass Spectrometry coupled analysis
The analysis conditions comprise a chromatographic column, an Agilent HP-5MS capillary column (specification: 30m × 0.32mm × 0.25 mu m), a split flow ratio: 30:1, a sample introduction amount: 1 mu L, a programmed temperature rise of 70 ℃ at an initial temperature, 3min at a temperature rise rate of 5 ℃/min, 160 ℃ at a temperature rise rate of 5 ℃/min, 10min at a temperature rise rate of 10 ℃/min, a carrier gas: helium, a carrier gas flow rate: 0.8m L/min, a sample injection port temperature: 280 ℃, a transmission line temperature: 280 ℃, a solvent delay: 3.5min, an ionization mode: EI, an ionization energy: 70eV, an ion source temperature: 230 ℃, a quadrupole rod temperature: 150 ℃, a scanning mode: Scan mode, and a scanning range of 35-500 amu.
And (4) performing retrieval and qualitative by adopting an NIST spectral library, and quantifying by using an internal standard relative peak area method.
2.3 establishing the fingerprint of the content of the popping beads for the cigarette, which has the same specific steps as the embodiment 1.
The similarity of the bead blasting samples of different batches is calculated according to a formula, the similarity is over 0.9, and the quality stability of the bead blasting samples of different batches is better.
Example 3
1. Materials, reagents and apparatus were the same as in example 1.
2.1 treatment of the samples
Grinding a bead blasting sample by using a mortar, taking the contents of the bead blasting sample to be reserved after filtering the contents of the bead blasting sample by using a 0.22 mu m organic phase needle filter membrane, accurately transferring 1.0m L bead blasting contents into a 50m L triangular flask by using a liquid transfer gun, adding 10.0m L n-hexane solution containing n-heptadecane, oscillating and extracting for 60min, standing, taking the supernatant to pass through the organic phase filter membrane, and analyzing by using a gas chromatography-mass spectrometry combination method, wherein the concentration of the n-hexane solution containing the n-heptadecane is 0.2mg/m L, so that the ratio of the contents of the bead blasting to the internal standard substance in the internal standard solution is 1m L: 2 mg.
2.2 gas chromatography-Mass Spectrometry analysis
The analysis conditions comprise a chromatographic column, an Agilent HP-5MS capillary column (specification: 30m × 0.32mm × 0.25 mu m), a split flow ratio: 5:1, a sample introduction amount: 1 mu L, a programmed temperature rise of 80 ℃, a temperature rise rate of 5 ℃/min to 160 ℃, a temperature rise rate of 10 ℃/min to 280 ℃, a temperature rise rate of 10 ℃/min to 10min, a carrier gas: helium, a carrier gas flow rate: 1.2m L/min, a sample inlet temperature: 280 ℃, a transmission line temperature: 280 ℃, a solvent delay of 3.5min, an ionization mode: EI, an ionization energy: 70eV, an ion source temperature: 230 ℃, a quadrupole temperature: 150 ℃, a scanning mode: Scan mode, and a scanning range of 35-500 amu.
And (4) performing retrieval and qualitative by adopting an NIST spectral library, and quantifying by using an internal standard relative peak area method.
2.3 establishing the fingerprint of the content of the popping beads for the cigarette, which has the same specific steps as the embodiment 1.
The SPSS19.0 software is adopted to perform systematic clustering analysis on fingerprint data of different batches, dilution samples and mixing samples of the cigarette bead blasting samples, and the result shows that the systematic clustering analysis can distinguish different batches, dilution samples and mixing samples of the bead blasting samples, and the systematic clustering analysis method can be used for bead blasting quality stability evaluation.
The method adopts a normal hexane oscillation extraction and gas chromatography-mass spectrometry combined method to obtain a fingerprint chromatogram of the tobacco bead blasting inclusion sample, establishes a chromatography-fingerprint chromatogram of the tobacco bead blasting inclusion, evaluates the quality stability of the tobacco bead blasting inclusion by comparing the Euclidean distance, the included angle cosine, the Euclidean distance ratio and the similarity of various batches of tobacco bead blasting inclusions and blended and diluted samples, and can obviously distinguish the tobacco bead blasting inclusion sample from the blended and diluted samples by utilizing a cluster analysis method. The result shows that the chromatographic fingerprint spectrum method is combined with clustering analysis to effectively judge the inherent quality stability of the bead blasting for the cigarettes and provide technical support and reference for the evaluation research of the quality stability of the bead blasting for the cigarettes.
Claims (6)
1. A method for evaluating the internal quality stability of a cigarette bead is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively grinding a plurality of batches of bead blasting samples for cigarettes, then carrying out membrane filtration to obtain bead blasting inclusions, adding an internal standard solution into the bead blasting inclusions, extracting, and then taking supernatant fluid to carry out membrane filtration, wherein the ratio of the bead blasting inclusions to the internal standard in the internal standard solution is 1m L (0.5-2.0) mg, the ground membrane filtration is carried out through a 0.22 mu m or 0.45 mu m organic phase needle filter membrane, and the internal standard solution is n-hexane solution of n-heptadecane;
(2) analyzing the supernatant after the film passing by adopting a gas chromatography-mass spectrometry combined method, determining a common peak by taking an internal standard peak as a reference peak, determining the relative retention time α and the relative peak area S value of the chromatographic peak in the bead blasting sample for the tobacco, and establishing a chromatographic fingerprint of each bead blasting inclusion sample, wherein the conditions in the analysis of the gas chromatography-mass spectrometry combined method are that a chromatographic column is an Agilent HP-5MS capillary column with the specification of 30m × 0.32mm × 0.25.25 mu m, the split ratio is (5-30): 1, the sample injection amount is 1 mu L, the temperature is programmed to be increased to the initial temperature of 60-80 ℃ and maintained for 3min, then the temperature is increased to 160 ℃ at the heating rate of 5 ℃/min, then the temperature is increased to 280 ℃ at the heating rate of 10 ℃/min, the flow is maintained for 10min, the carrier gas is helium, the carrier gas flow rate is 0.8-1.2 m L/min, the sample injection port temperature is 280 ℃, the transmission line temperature is 280 ℃, the solvent ionization delay is 3.5min, the ionization energy is 70 ℃, the ionization energy is scanned by a four-grade rod ion source, and the scanning is performed in a scanning mode of 500-150 ℃ in a Scan mode;
(3) the method comprises the steps of respectively obtaining Euclidean distance, Euclidean distance ratio and similarity by utilizing the S value of the relative peak area of each component of each batch of cigarette bead blasting samples, evaluating the internal quality stability of the cigarette bead blasting, specifically carrying out cluster analysis on the chromatographic fingerprint spectrum of each bead blasting content sample, measuring by using the Euclidean distance, connecting every two samples by using an inter-class average chain lock method, outputting a system cluster analysis dendrogram, taking the abscissa of the system cluster analysis dendrogram as a critical value, and judging the quality stability of different batches of samples of the cigarette bead blasting according to the size of the critical value.
2. The method for evaluating the inherent quality stability of the blasting bead for the cigarette according to claim 1, which is characterized in that: in the step (1), oscillation extraction is adopted for extraction, and the extraction time is 20-60 min.
3. The method for evaluating the inherent quality stability of the blasting bead for the cigarette according to claim 1, which is characterized in that: in the gas chromatography-mass spectrometry combined analysis, an NIST (NIST standard) library is adopted for retrieval and qualitative determination, and an internal standard relative peak area method is adopted for quantification.
4. The method for evaluating the internal quality stability of the cigarette blasting bead according to the claim 1, wherein in the step (2), the calculation formula of the relative retention time α and the relative peak area S value is as follows:
α＝tr/tis(1)
S＝Sr/Sis(2)
wherein, trIs the retention time of the peak to be measured; t is tisIs the retention time of the internal standard; s is the relative peak area; srIs the peak area of each sample component; sisIs the peak area of the internal standard.
5. The method for evaluating the inherent quality stability of the blasting bead for the cigarette according to claim 4, which is characterized in that: assuming that the number k of characteristic peaks is 1, 2, …, m, in step (3), the calculation formula of euclidean distance, euclidean distance ratio and similarity is:
similarity is equal to Euclidean distance ratio × included angle cosine value (6)
Wherein d is the Euclidean distance; xkIs S of the kth peak of sample Xr；XrIs the kth peak S of the batch samplerThe mean value of (a); c is the cosine of the included angle; y iskIs S of the kth peak of sample Yr。
6. The method for evaluating the inherent quality stability of the blasting bead for the cigarette according to claim 1, which is characterized in that: respectively diluting and blending essence and spice into the contents of the blasting beads, respectively adding an internal standard solution, extracting, taking supernatant fluid to pass through a membrane, and performing gas chromatography-mass spectrometry combined analysis to obtain a chromatographic fingerprint of a diluted sample and a chromatographic fingerprint of a blended sample; in the step (3), the chromatographic fingerprint of each explosive inclusion sample, the chromatographic fingerprint of the diluted sample and the chromatographic fingerprint of the blended sample are subjected to cluster analysis.
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| CN108548877B (en) * | 2018-04-03 | 2021-12-28 | 陕西中烟工业有限责任公司 | Method for measuring volatile components of bead blasting for cigarettes by solid phase microextraction-gas chromatography-mass spectrometry technology |
| CN109142258A (en) * | 2018-07-27 | 2019-01-04 | 重庆中烟工业有限责任公司 | A kind of cigarette quick-fried pearl identification classification method |
| CN109142570A (en) * | 2018-08-14 | 2019-01-04 | 广东中烟工业有限责任公司 | A kind of the cigarette extraction of flavor component and content assaying method in quick-fried pearl |
| CN109358022A (en) * | 2018-11-22 | 2019-02-19 | 陕西中烟工业有限责任公司 | A kind of method of the quick-fried pearl type of quick discrimination cigarette |
| CN109580832B (en) * | 2018-12-29 | 2021-11-09 | 陕西中烟工业有限责任公司 | Flash evaporation-GC/MS (gas chromatography/mass spectrometry) rapid detection method for cigarette blasting inclusion |
| CN110824050A (en) * | 2019-11-15 | 2020-02-21 | 湖北中烟工业有限责任公司 | Method for evaluating quality stability of tipping paper for cigarettes |
| CN112641130B (en) * | 2020-12-25 | 2022-08-12 | 福建金闽再造烟叶发展有限公司 | Cigarette bead blasting quality control method |
| CN113049709A (en) * | 2021-03-23 | 2021-06-29 | 江苏中烟工业有限责任公司 | Method for screening characteristic markers in bead blasting for cigarettes and quality control method |
| CN113984939A (en) * | 2021-10-27 | 2022-01-28 | 江苏中烟工业有限责任公司 | Method for screening aroma markers in bead-blasting essence |
| CN115406983A (en) * | 2022-08-16 | 2022-11-29 | 浙江中烟工业有限责任公司 | Method for measuring breaking time of blasting beads in cigarette filter |
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