CN105136947A - Method of accurately representing and evaluating fruit smell character in fragrance of tobacco - Google Patents
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- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 8
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- 229940020436 gamma-undecalactone Drugs 0.000 claims description 8
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- 239000012086 standard solution Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
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- 238000011067 equilibration Methods 0.000 claims description 6
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 6
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 6
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 6
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- 239000001674 (E)-1-(2,6,6-trimethyl-1-cyclohexenyl)but-2-en-1-one Substances 0.000 claims description 5
- BGTBFNDXYDYBEY-UHFFFAOYSA-N 1-(2,6,6-trimethylcyclohexen-1-yl)but-2-en-1-one Chemical compound CC=CC(=O)C1=C(C)CCCC1(C)C BGTBFNDXYDYBEY-UHFFFAOYSA-N 0.000 claims description 5
- POIARNZEYGURDG-UHFFFAOYSA-N beta-damascenone Natural products CC=CC(=O)C1=C(C)C=CCC1(C)C POIARNZEYGURDG-UHFFFAOYSA-N 0.000 claims description 5
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Abstract
Description
技术领域 technical field
本发明属于卷烟感官质量评价和分析技术领域,具体是涉及一种能够准确表征和评价卷烟香气中的果香特征的方法。 The invention belongs to the technical field of cigarette sensory quality evaluation and analysis, and in particular relates to a method capable of accurately characterizing and evaluating the fruity aroma feature in cigarette aroma.
背景技术 Background technique
作为一种燃吸消费品,卷烟的感官质量是其核心和灵魂,因此对卷烟感官质量的评价和分析一直是卷烟技术工作中最为重要的内容之一。文献调研表明,近年来围绕卷烟感官质量开展了大量的技术研发,总结起来可以分为卷烟感官质量评价、与感官质量相关的物质分析两种类型。 As a burning and smoking consumer product, the sensory quality of cigarettes is its core and soul, so the evaluation and analysis of cigarette sensory quality has always been one of the most important contents in cigarette technology work. The literature survey shows that in recent years, a large number of technical research and development have been carried out around the sensory quality of cigarettes, which can be summarized into two types: evaluation of cigarette sensory quality and analysis of substances related to sensory quality.
1、卷烟感官质量评价 1. Evaluation of sensory quality of cigarettes
现行的卷烟感官质量评价方法有两种,一种是对卷烟感官品质的综合评价,另一种是对卷烟感官风格特征及品质特征的评价。 There are currently two methods for evaluating the sensory quality of cigarettes, one is the comprehensive evaluation of the sensory quality of cigarettes, and the other is the evaluation of the sensory style and quality characteristics of cigarettes.
卷烟感官品质的综合评价方法:GB5606.4-2005《卷烟第4部分:感官技术要求》中所规定的,感官评吸的六项评判标准,包括光泽、香气、谐调、杂气、刺激性及余味; Comprehensive evaluation method for the sensory quality of cigarettes: as stipulated in GB5606.4-2005 "Cigarette Part 4: Sensory Technical Requirements", six evaluation criteria for sensory evaluation, including gloss, aroma, harmony, miscellaneous gas, irritation and Aftertaste;
卷烟感官风格特征及品质特征评价方法:YC/T497-2014《卷烟中式卷烟风格感官评价方法》中将卷烟感官香气风格进一步细分为:清香、果香、辛香、木香、青滋香、花香、药草香、豆香、可可香、奶香、膏香、烘焙香、甜香、烤烟烟香和晾晒烟烟香等15个香韵指标; Cigarette sensory style characteristics and quality characteristics evaluation method: YC/T497-2014 "Cigarette Chinese Cigarette Style Sensory Evaluation Method" further subdivides the sensory aroma style of cigarettes into: fresh fragrance, fruity fragrance, spicy fragrance, woody fragrance, green fragrance, 15 aroma indicators such as flower aroma, herbal aroma, bean aroma, cocoa aroma, milk aroma, paste aroma, baking aroma, sweet aroma, flue-cured tobacco aroma and air-cured tobacco aroma;
上述两种现行评价方法都是从评吸者视觉、嗅觉、味觉等主观经验感受出发建立的评价和分析方法,其中GB5606.4-2005主要应用于卷烟产品感官质量的符合性检验,而YC/T497-2014则应用于卷烟产品感官质量的一致性检验。但这两种方法需要依赖卷烟感官质量评委的经验进行,容易受到评委的专业水平、评吸技能、主观喜好等多方面因素的影响,不同评委的评价结果有可能出现较大差异。 The above two current evaluation methods are evaluation and analysis methods established based on the subjective experience of smokers such as vision, smell, and taste. Among them, GB5606.4-2005 is mainly used in the compliance inspection of the sensory quality of cigarette products, while YC/ T497-2014 is applied to the consistency test of the sensory quality of cigarette products. However, these two methods need to rely on the experience of the judges of the sensory quality of cigarettes, and are easily affected by various factors such as the professional level of the judges, smoking evaluation skills, subjective preferences, etc., and the evaluation results of different judges may vary greatly.
2、与卷烟感官质量相关的物质分析 2. Analysis of substances related to the sensory quality of cigarettes
随着检测技术的不断进步,研究人员采用顶空固相微萃取-GC/MS、LC-MS、传感器、电子鼻、近红外等技术手段对与卷烟感官质量相关的致香物质进行了检测,并对致香物质浓度及其致香贡献进行多元回归,通过建立相应的回归方程来寻找不同浓度的物质对卷烟感官香气的影响。例如CN201210388661一种卷烟香型的检测判定方法。回归方程虽然可以在一定程度上解释致香物质的浓度与卷烟香气之间的相关性。但是GC-MS方法在物质定性/定量上存在着灵敏度低、分辨率不足、选择性差、易产生假阳性结果、且不能给出足够的定性/定量信息等问题,致使定性/定量结果存在很大不确定性。同时,相关的研究工作也无法解释突厥烯酮、异丁酸甲酯等含量低,却对感官香气贡献大(即阈值低)的物质对卷烟果香香气风格的显著作用;缺少对卷烟品质特征及风格特征基于物质基础的相应描述和表达,许多感官评吸特征也无法从物质基础上予以解释。 With the continuous improvement of detection technology, researchers have used headspace solid-phase microextraction-GC/MS, LC-MS, sensors, electronic nose, near-infrared and other technical means to detect the aroma-causing substances related to the sensory quality of cigarettes. The multivariate regression was carried out on the concentration of aroma-causing substances and their aroma-causing contributions, and the influence of different concentrations of substances on the sensory aroma of cigarettes was found by establishing corresponding regression equations. For example, CN201210388661 discloses a method for detecting and judging cigarette flavor type. Although the regression equation can explain the correlation between the concentration of aromatizing substances and cigarette aroma to a certain extent. However, the GC-MS method has problems such as low sensitivity, insufficient resolution, poor selectivity, easy to produce false positive results, and insufficient qualitative/quantitative information in the qualitative/quantitative aspects of substances, resulting in large gaps in qualitative/quantitative results. Uncertainty. At the same time, relevant research work cannot explain the significant effect of substances such as turkelenone and methyl isobutyrate that are low in content but have a large contribution to sensory aroma (ie, low threshold) on the fruity aroma style of cigarettes; lack of influence on cigarette quality characteristics And style features are based on the corresponding description and expression of the material basis, and many sensory evaluation characteristics cannot be explained from the material basis.
3、小结 3. Summary
现有的评价与分析方法均存在一定缺陷。如何通过化学分析技术手段对“卷烟风格特征及品质特征”进行准确评价与分析,就成为烟草行业科技工作者们所面临亟待解决的重大课题之一。但现有技术中尚未见有很好地解决办法。 Existing evaluation and analysis methods have certain defects. How to accurately evaluate and analyze "cigarette style characteristics and quality characteristics" through chemical analysis techniques has become one of the major issues facing the scientific and technological workers in the tobacco industry. But there is not yet a good solution in the prior art.
发明内容 Contents of the invention
本发明的目的在于针对现有技术的不足,提供一种能够准确表征和评价卷烟香气中的果香特征的方法。通过顶空-气相色谱-串联质谱法(HS-GC-MS/MS)检测获取致香物质定量数据,并通过相应致香物质的阈值来计算并构建得到卷烟的果香香韵指数G,对卷烟果香香气风格特征进行评判,以避免感官评吸造成的主观误差。 The object of the present invention is to provide a method capable of accurately characterizing and evaluating the fruity aroma feature in cigarette aroma aiming at the deficiencies of the prior art. Quantitative data of aroma-inducing substances were obtained by headspace-gas chromatography-tandem mass spectrometry (HS-GC-MS/MS), and the fruity aroma index G of cigarettes was calculated and constructed through the threshold value of corresponding aroma-inducing substances. To avoid subjective errors caused by sensory evaluation and smoking.
本发明的目的通过以下技术方案实现。 The purpose of the present invention is achieved through the following technical solutions.
除非另有说明,本发明所采用的百分数均为质量百分数。 Unless otherwise specified, the percentages used in the present invention are all mass percentages.
一种准确表征和评价卷烟香气中果香特征的方法,包括以下步骤: A method for accurately characterizing and evaluating fruity aroma characteristics in cigarette aroma, comprising the following steps:
(1)以甲酸乙酯、乙酸戊酯、乙酸异丁酯、异丁酸乙酯、戊酸乙酯、γ-十一内酯(桃醛)、二氢猕猴桃内酯、异戊酸异戊酯、二氢大马酮、香叶基丙酮、突厥烯酮和苯甲醛作为显著影响卷烟果香香气风格的12种特征物质; (1) Ethyl formate, amyl acetate, isobutyl acetate, ethyl isobutyrate, ethyl valerate, γ-undecalactone (peach aldehyde), dihydroactidolactone, isoamyl isovalerate Esters, damascenone, geranyl acetone, turkelenone and benzaldehyde as 12 characteristic substances that significantly affect the fruity aroma style of cigarettes;
(2)特征物质标准工作曲线的建立: (2) Establishment of standard working curves for characteristic substances:
①标准储备液:分别准确称取10.0mg的特征物质标准品,置于同一个100mL容量瓶中,用无水乙醇溶解并稀释定容,配制成质量浓度为100μg/mL的混合标准储备液,贮存在4℃冰箱中备用; ①Standard stock solution: Accurately weigh 10.0mg of characteristic substance standard respectively, place them in the same 100mL volumetric flask, dissolve and dilute to volume with absolute ethanol, and prepare a mixed standard stock solution with a mass concentration of 100 μg/mL, Store in a refrigerator at 4°C for later use;
②内标物萘溶于无水乙醇,浓度为100μg/mL; ② The internal standard naphthalene was dissolved in absolute ethanol at a concentration of 100 μg/mL;
③分别移取①中储备液0.1mL、0.5mL、1mL、5mL、10mL,分别置于5个100mL容量瓶中,分别加入1mL内标溶液,用无水乙醇稀释得到浓度依次为0.1μg/mL、0.5μg/mL、1μg/mL、5μg/mL、10μg/mL的化合物溶液,其中内标萘浓度为1μg/mL,作为工作标准溶液备用; ③Respectively pipette 0.1mL, 0.5mL, 1mL, 5mL and 10mL of the stock solution in ①, place them in five 100mL volumetric flasks respectively, add 1mL of internal standard solution, and dilute with absolute ethanol to obtain a concentration of 0.1μg/mL in sequence , 0.5 μg/mL, 1 μg/mL, 5 μg/mL, and 10 μg/mL compound solutions, in which the internal standard naphthalene concentration is 1 μg/mL, as the working standard solution for later use;
④分别用12个特征物质的标准样品及内标的响应值比值与其浓度比值进行线性回归,得到每一种特征物质的标准工作曲线,曲线强制归零,线性相关系数R2须大于0.999; ④ Perform linear regression with the response value ratio of 12 standard samples of characteristic substances and internal standard and their concentration ratio to obtain the standard working curve of each characteristic substance, the curve is forced to zero, and the linear correlation coefficient R2 must be greater than 0.999;
(3)待测样品的前处理: (3) Pretreatment of samples to be tested:
a、取待测样品的烟丝,按照《YC/T31烟草及烟草制品试样的制备和水分测定烘箱法》进行水分测定; a. Take the shredded tobacco of the sample to be tested, and perform moisture determination according to "YC/T31 Tobacco and Tobacco Products Sample Preparation and Moisture Determination Oven Method";
b、称取1.000g待测样品的烟丝,置于20mL顶空瓶中,加入1mL内标溶液,迅速压紧瓶盖,振摇使烟丝均匀而松散地平铺于瓶底; b. Weigh 1.000g of shredded tobacco of the sample to be tested, put it in a 20mL headspace bottle, add 1mL of internal standard solution, quickly press the cap of the bottle, and shake to spread the shredded tobacco evenly and loosely on the bottom of the bottle;
(4)致香物质仪器分析条件 (4) Instrumental analysis conditions for aroma-causing substances
①顶空仪分析条件: ①Headspace analysis conditions:
顶空瓶容量:20mL,样品环容量:3mL,样品平衡温度:100℃,样品环温度:120℃,传输线温度:160℃,样品平衡时间:45min,GC循环时间:70min,样品瓶加压压力:138KPa,加压时间:0.20min,充气时间:0.20min,样品环平衡时间:0.05min,进样时间:0.50min; Headspace vial capacity: 20mL, sample loop capacity: 3mL, sample equilibration temperature: 100°C, sample loop temperature: 120°C, transfer line temperature: 160°C, sample equilibration time: 45min, GC cycle time: 70min, vial pressurization pressure : 138KPa, pressurization time: 0.20min, inflation time: 0.20min, sample loop equilibrium time: 0.05min, sample injection time: 0.50min;
②色谱分析条件: ② Chromatographic analysis conditions:
DB-5MS毛细管柱;进样口温度:250℃;恒流模式,柱流量1mL/min;分流比:20:1;升温程序:初始温度50℃,保持2min,以5℃/min的速率升温至200℃,保持10min,最后再以10℃/min的速率升温至250℃,保持20min; DB-5MS capillary column; inlet temperature: 250°C; constant flow mode, column flow rate: 1mL/min; split ratio: 20:1; heating program: initial temperature 50°C, hold for 2min, then increase temperature at a rate of 5°C/min to 200°C, keep for 10min, and finally raise the temperature to 250°C at a rate of 10°C/min, and keep for 20min;
③质谱分析条件: ③Mass spectrometry analysis conditions:
EI电离模式,电离能70ev;灯丝电流:80μA;离子源温度:170℃;传输线温度:250℃;Q2碰撞气:氩气纯度99.999%,CID气体压力为1.5mtorr;扫描方式:多反应监测MRM模式,对每个离子的检测时间为150ms; EI ionization mode, ionization energy 70ev; filament current: 80μA; ion source temperature: 170°C; transfer line temperature: 250°C; Q2 collision gas: argon purity 99.999%, CID gas pressure 1.5mtorr; scanning method: multiple reaction monitoring MRM mode, the detection time for each ion is 150ms;
有关定性离子对、定量离子对以及优化后的碰撞能量(CE)值如表1所示: The relevant qualitative ion pairs, quantitative ion pairs and optimized collision energy (CE) values are shown in Table 1:
表1: Table 1:
(5)读取待测烟丝样品中各特征物质的响应值,用步骤(2)所建立的标准曲线对待测样品中各特征物质初始数据进行校正,即得到待测样品中某一种特征物质的含量Ci: (5) Read the response value of each characteristic substance in the shredded tobacco sample to be tested, and use the standard curve established in step (2) to correct the initial data of each characteristic substance in the sample to be tested, that is, to obtain a certain characteristic substance in the sample to be tested Content C i :
其中,Ci表示待测样品中某一种特征物质的含量,单位为ug/g; Among them, C i represents the content of a certain characteristic substance in the sample to be tested, and the unit is ug/g;
Ai为待测样品中某一种特征物质的峰面积,单位为U(积分单位); A i is the peak area of a certain characteristic substance in the sample to be tested, and the unit is U (integral unit);
As为内标物质的峰面积,单位为U(积分单位); A s is the peak area of the internal standard substance, and the unit is U (integral unit);
ms为加入内标物质的量,单位为ug; m s is the amount of internal standard substance added, the unit is ug;
m为称取烟丝质量,单位为g; m is the mass of shredded tobacco, in g;
w为待测烟丝水分含量,单位为%; w is the moisture content of cut tobacco to be tested, in %;
Ki为各特征物质的标准工作曲线斜率; K i is the slope of the standard working curve of each characteristic substance;
(6)卷烟果香香韵指数G的计算: (6) Calculation of Cigarette Fruity Flavor Index G:
12种特征物质对卷烟烟气果香均有贡献,通过气味活度值OAV来评价某一特征物质对卷烟果香的贡献程度,卷烟果香香韵指数模型是12种特征物质气味活度值的加和: The 12 characteristic substances contribute to the fruity aroma of cigarette smoke. The contribution of a certain characteristic substance to the fruity aroma of cigarettes is evaluated by the odor activity value OAV. The cigarette fruity aroma index model is the odor activity value of the 12 characteristic substances sum of:
卷烟果香香韵指数
式中:Ci为i种特征物质的含量;ti为i种特征物质的香气阈值;Oi为i种特征物质的OAV值,即n为特征物质的数目;因香味阈值很低,为便于和感官评价结果比较,将各个特征物质的OAV值乘以一个系数,fi为各个物质的修正系数,具体如表2所示; In the formula: C i is the content of i characteristic substances; t i is the aroma threshold of i characteristic substances; O i is the OAV value of i characteristic substances, namely n is the number of characteristic substances; because the fragrance threshold is very low, in order to facilitate the comparison with the sensory evaluation results, the OAV value of each characteristic substance is multiplied by a coefficient, and f i is the correction coefficient of each substance, as shown in Table 2;
表2 Table 2
(7)卷烟果香香气风格特征评判: (7) Judgment on the characteristics of cigarette fruity aroma style:
按照表3的评分标准对卷烟香气进行评判; Judge the cigarette aroma according to the scoring criteria in Table 3;
表3卷烟果香香气风格评判标准 Table 3 Criteria for Judging the Fruity Aroma Style of Cigarettes
卷烟香气中的果香特征与卷烟果香香韵指数G呈正相关关系,即卷烟果香香韵指数G值越高,则表明该卷烟的果香香气风格越显著。 The fruity aroma feature in the cigarette aroma is positively correlated with the cigarette fruity aroma index G, that is, the higher the cigarette fruity aroma index G value, the more significant the fruity aroma style of the cigarette.
相对于现有技术,本发明具有以下优点: Compared with the prior art, the present invention has the following advantages:
1、本发明以卷烟风格特征指标—果香香韵为导向,采用HS-GC-MS/MS技术手段,在建立品质特征及风格特征物质谱库的基础上,对卷烟品质、风格相关物质进行定性、定量检测;利用检测结果采用统计模型建立果香香韵指数的数学表达式,该表达式综合以相应的阈值计算并构建表征卷烟果香香气风格的指数(果香香韵指数G),来综合表征及评价卷烟产品的果香香气风格。果香香韵指数G模型的提出从物质基础的角度对卷烟果香特征进行了相应描述和表达,从物质基础上解释了许多感官评吸特征,解释了突厥烯酮、异丁酸甲酯等含量低,却对感官香气贡献大(即阈值低)的物质对卷烟果香香气风格的显著作用。而且避免了感官评吸的主观性,客观综合表征及评价卷烟产品的果香香气风格。 1. The present invention is guided by the characteristic index of cigarette style - fruity aroma, adopts HS-GC-MS/MS technical means, and on the basis of establishing the quality characteristic and style characteristic material spectrum library, the quality and style related substances of cigarettes are analyzed Qualitative and quantitative detection; use the test results to establish the mathematical expression of the fruity aroma index by using the statistical model, and the expression is comprehensively calculated with the corresponding threshold value to construct an index (fruity aroma index G) representing the style of cigarette fruity aroma, To comprehensively characterize and evaluate the fruity aroma style of cigarette products. The fruity aroma index G model is proposed to describe and express the fruity aroma characteristics of cigarettes from the perspective of material basis, explain many sensory evaluation characteristics from the material basis, and explain the characteristics of turkelenone, methyl isobutyrate, etc. Substances with low content but large contribution to sensory aroma (that is, low threshold) have a significant effect on the fruity aroma style of cigarettes. Moreover, the subjectivity of sensory evaluation and smoking is avoided, and the fruity aroma style of cigarette products is objectively and comprehensively characterized and evaluated.
2、顶空-气相色谱-串联质谱法(HS-GC-MS/MS)操作简便、不易受杂质干扰、检测结果更为准确。气相色谱-串联质谱法(GC-MS/MS)的选择性和灵敏度比气质联用法(GC-MS)高,避免了GC-MS灵敏度低、分辨率不足、选择性差、易产生假阳性结果、且不能给出足够的定性/定量信息等问题。 2. Headspace-gas chromatography-tandem mass spectrometry (HS-GC-MS/MS) is easy to operate, less susceptible to impurity interference, and more accurate detection results. The selectivity and sensitivity of gas chromatography-tandem mass spectrometry (GC-MS/MS) are higher than those of gas chromatography-mass spectrometry (GC-MS), which avoids the low sensitivity, insufficient resolution, poor selectivity and false positive results of GC-MS. And can not give enough qualitative / quantitative information and other issues.
具体实施方式 Detailed ways
为了更好地理解本发明,下面通过实施例对本发明做进一步地详细说明,但实施例并不是对本发明技术方案的限定。 In order to better understand the present invention, the present invention will be further described in detail through the following examples, but the examples are not intended to limit the technical solution of the present invention.
实施例1: Example 1:
(一)材料与仪器: (1) Materials and instruments:
(1)材料:某品牌卷烟A; (1) Material: cigarette A of a certain brand;
试剂:无水乙醇(AR,上海试剂一厂);甲酸乙酯、乙酸戊酯、乙酸异丁酯、异丁酸乙酯、戊酸乙酯、γ-十一内酯(桃醛)、二氢猕猴桃内酯、异戊酸异戊酯、二氢大马酮、香叶基丙酮、突厥烯酮、苯甲醛、萘(纯度均大于98%,均购自百灵威)。 Reagents: absolute ethanol (AR, Shanghai Reagent No. 1 Factory); ethyl formate, amyl acetate, isobutyl acetate, ethyl isobutyrate, ethyl valerate, γ-undecalactone (peach aldehyde), di Hydroactinolactone, isopentyl isovalerate, damascenone, geranylacetone, turkenone, benzaldehyde, naphthalene (purity greater than 98%, all purchased from Bailingwei).
(2)仪器:AG204电子天平(感量:0.0001g,瑞士METTLERTOLEDO公司);鼓风恒温干燥箱(101A-2,上海市实验仪器总厂);顶空仪(G1888,Agilent);GC-MS/MS(SCION456GC-TQ,Bruker公司);移液枪(Tripette公司)。 (2) Instruments: AG204 electronic balance (sensitivity: 0.0001g, Swiss METTLERTOLEDO company); blast constant temperature drying oven (101A-2, Shanghai Experimental Instrument General Factory); headspace instrument (G1888, Agilent); GC-MS /MS (SCION456GC-TQ, Bruker Company); pipette gun (Tripette Company).
(二)试样的制备及特征物质的测定: (2) Preparation of samples and determination of characteristic substances:
(1)HS-GC-MS/MS法测定12种特征物质 (1) Determination of 12 characteristic substances by HS-GC-MS/MS method
A、样品制备:将成品卷烟A除去滤嘴,剥除接装纸,按照《YC/T31烟草及烟草制品试样的制备和水分测定烘箱法》进行水分测定; A. Sample preparation: Remove the filter tip from the finished cigarette A, peel off the tipping paper, and perform moisture determination according to "YC/T31 Tobacco and Tobacco Products Sample Preparation and Moisture Determination Oven Method";
将成品卷烟A除去滤嘴,剥除接装纸,使用分析天平称取1.000g烟丝(精确至0.1mg)于20mL顶空瓶中,加入1mL内标溶液,迅速压紧瓶盖,适当振摇使烟丝均匀而松散的平铺于瓶底。 Remove the filter tip from the finished cigarette A, peel off the tipping paper, weigh 1.000g of shredded tobacco (accurate to 0.1mg) into a 20mL headspace bottle with an analytical balance, add 1mL of internal standard solution, quickly press the bottle cap, and shake properly Spread the shredded tobacco evenly and loosely on the bottom of the bottle.
B、静态顶空条件为:顶空瓶容量:20mL,样品环容量:3mL,样品平衡温度:100℃,样品环温度:120℃,传输线温度:160℃,样品平衡时间:45min,GC循环时间:70min,样品瓶加压压力:138KPa,加压时间:0.20min,充气时间:0.20min,样品环平衡时间:0.05min,进样时间:0.50min;可以根据所选择的程序升温条件,适当调整GC循环时间; B. Static headspace conditions are: headspace bottle volume: 20mL, sample loop volume: 3mL, sample equilibration temperature: 100°C, sample loop temperature: 120°C, transfer line temperature: 160°C, sample equilibration time: 45min, GC cycle time : 70min, sample bottle pressurization pressure: 138KPa, pressurization time: 0.20min, inflation time: 0.20min, sample loop equilibrium time: 0.05min, sample injection time: 0.50min; can be adjusted appropriately according to the selected heating conditions GC cycle time;
C、在GC-MS/MS测定时,采用的色谱条件具体如下: C. When measuring by GC-MS/MS, the chromatographic conditions adopted are as follows:
a)色谱柱:DB-5MS弹性石英毛细管色谱柱(30m×0.25mm×0.25μm,美国Agilent公司);或其他等效色谱柱,如HP-5MS弹性石英毛细管色谱柱(30m×0.25mm×0.25μm)、MS(30m×0.25mm×0.25μm)等; a) Chromatographic column: DB-5MS elastic quartz capillary column (30m×0.25mm×0.25μm, Agilent, USA); or other equivalent chromatographic column, such as HP-5MS elastic quartz capillary column (30m×0.25mm×0.25 μm), MS (30m×0.25mm×0.25μm), etc.;
b)进样口温度:250℃; b) Injection port temperature: 250°C;
c)程序升温条件:初始温度50℃,保持2min,以5℃/min的速率升温至200℃,保持10min,最后再以10℃/min的速率升温至250℃,保持20min;可以根据样品的具体情况,选择其他合适的程序升温条件; c) Temperature programming conditions: initial temperature of 50°C, keep for 2min, raise the temperature to 200°C at a rate of 5°C/min, keep for 10min, and finally raise the temperature to 250°C at a rate of 10°C/min, and keep for 20min; In specific cases, select other suitable temperature programming conditions;
d)载气:He(纯度≥99.99%);Q2碰撞气:氩气(纯度99.999%)。 d) Carrier gas: He (purity ≥ 99.99%); Q2 collision gas: argon (purity 99.999%).
e)电离方式:EI源;电离能70ev;灯丝电流:80μA;离子源温度:170℃;传输线温度:250℃; e) Ionization method: EI source; ionization energy 70ev; filament current: 80μA; ion source temperature: 170°C; transmission line temperature: 250°C;
f)扫描方式:多反应监测MRM模式,CID气体压力为1.5mtorr;对每个离子的检测时间为150ms。 f) Scanning mode: multiple reaction monitoring MRM mode, CID gas pressure is 1.5mtorr; detection time for each ion is 150ms.
D、测定结果的计算:用HS-GC-MS/MS法测定一系列特征物质标准溶液,用特征物质与内标峰面积的比值作为纵坐标,特征物质的浓度与内标浓度的比值作为横坐标,分别建立12种特征物质的校正曲线,曲线强制归零。对校正数据进行线性回归,线性相关系数R2须大于0.999。 D. Calculation of measurement results: Measure a series of characteristic substance standard solutions by HS-GC-MS/MS method, use the ratio of the characteristic substance to the internal standard peak area as the vertical axis, and the ratio of the characteristic substance concentration to the internal standard concentration as the horizontal axis Coordinates, the calibration curves of the 12 characteristic substances were respectively established, and the curves were forced to zero. Perform linear regression on the calibration data, and the linear correlation coefficient R2 must be greater than 0.999.
测定样品,根据样品中的峰面积计算12种特征物质的含量,计算其中某一种特征物质的含量: Determine the sample, calculate the content of 12 characteristic substances according to the peak area in the sample, and calculate the content of one of the characteristic substances:
其中,Ci表示检测分析得到的特征物质的含量,单位为ug/g; Among them, C i represents the content of the characteristic substance obtained by detection and analysis, and the unit is ug/g;
Ai为试样中特征物质的峰面积,单位为U(积分单位); A i is the peak area of the characteristic substance in the sample, and the unit is U (integral unit);
As为内标物质的峰面积,单位为U(积分单位); A s is the peak area of the internal standard substance, and the unit is U (integral unit);
ms为加入内标物质的量,单位为ug; m s is the amount of internal standard substance added, the unit is ug;
m为称取烟丝质量,单位为g; m is the mass of shredded tobacco, in g;
w为待测烟丝水分含量,单位为%; w is the moisture content of cut tobacco to be tested, in %;
ki为各特征物质工作曲线斜率。 ki is the slope of the working curve of each characteristic substance.
E、测定结果: E. Measurement results:
(1)某品牌烟丝样品A按照所述的方法进行样品制备,用HS-GC-MS/MS法测定其12种特征物质含量。结果见表4: (1) Cut tobacco sample A of a certain brand was prepared according to the method described, and the contents of 12 characteristic substances were determined by HS-GC-MS/MS method. The results are shown in Table 4:
表4HS-GC-MS/MS法测定A品牌卷烟中12种特征物质(ug/g)的结果 Table 4 The results of HS-GC-MS/MS determination of 12 characteristic substances (ug/g) in A brand cigarettes
(2)A品牌卷烟果香香韵指数(GA)的计算: (2) Calculation of the fruity aroma index (G A ) of brand A cigarettes:
基于上述测定结果,带入下面的公式: Based on the above measurement results, the following formula is brought in:
卷烟果香香韵指数
式中:Ci为i种特征物质的含量;ti为i种特征物质的香气阈值;Oi为i种特征物质的OAV值,即n为特征物质的数目;为便于和感官评价结果比较,将各个特征物质的OAV值乘以一个系数,fi为各物质的OAV修正系数。12种特征物质的气味活度值如表5所示。 In the formula: C i is the content of i characteristic substances; t i is the aroma threshold of i characteristic substances; O i is the OAV value of i characteristic substances, namely n is the number of characteristic substances; in order to facilitate the comparison with the sensory evaluation results, the OAV value of each characteristic substance is multiplied by a coefficient, and f i is the OAV correction coefficient of each substance. The odor activity values of the 12 characteristic substances are shown in Table 5.
表5A品牌卷烟烟丝中12种特征物质的气味活度值(Oi) Table 5 Odor activity values of 12 characteristic substances in shredded tobacco of brand cigarettes (O i )
A品牌卷烟果香香韵指数(GA)=3.93。 Fruity aroma index (G A ) of brand A cigarettes = 3.93.
GA表明该品牌卷烟果香香气风格较强。 G A indicates that the brand's cigarettes have a strong fruity aroma style.
实施例2: Example 2:
重复实施例1的过程,选择另一品牌卷烟B,用HS-GC-MS/MS法测定其12种特征物质含量,测定值如表6所示,12种特征物质的气味活度值如表7所示。 Repeat the process of embodiment 1, select another brand cigarette B, measure its 12 kinds of characteristic substance contents with HS-GC-MS/MS method, measured value is as shown in table 6, and the odor activity value of 12 kinds of characteristic substances is as shown in table 7.
表6HS-GC-MS/MS法测定B品牌卷烟中12种特征物质(ug/g)的结果 Table 6 The results of HS-GC-MS/MS determination of 12 characteristic substances (ug/g) in B brand cigarettes
表7B品牌卷烟烟丝中12种特征物质的气味活度值(Oi) Table 7 Odor activity values of 12 characteristic substances in shredded tobacco of B brand cigarettes (O i )
B品牌卷烟果香香韵指数(GB)=3.87 Fruity fragrance index of brand B cigarettes (G B )=3.87
GB表明该品牌卷烟卷烟果香香气风格较强,但比A品牌卷烟果香香气风格较弱。 G B indicates that the fruity aroma style of cigarettes of this brand is stronger, but weaker than that of A brand cigarettes.
实施例3: Example 3:
组织14名具有全国卷烟感官评吸资格证书的技术人员对A、B两品牌卷烟样品的香气风格指标(烤烟烟香、晾晒烟烟香、清香、果香、辛香、木香、青滋香、花香、药草香等)进行评价,得到果香指标评判分值。结果如表8所示。 Organize 14 technicians with the national cigarette sensory evaluation qualification certificate to test the aroma style indicators of A and B brands of cigarette samples (flue-cured tobacco aroma, air-dried tobacco aroma, fresh aroma, fruity aroma, spicy aroma, woody aroma, and green aroma) , flower fragrance, medicinal herb fragrance, etc.) to evaluate and obtain the fruity fragrance index evaluation score. The results are shown in Table 8.
表8A和B两个品牌卷烟的果香香韵指数和感官评价值 Table 8 Fruity flavor index and sensory evaluation value of two brands of cigarettes A and B
从表8可知,实施例1-2所得出的果香香韵指数与果香指标感官评价分值没有显著差异,证明了本发明所提出的表征和评价卷烟香气中果香特征的方法的准确可行性。而且在实施过程中,可以避免常规感官评价方法的主观性,能更客观的对卷烟果香香气风格进行表征和评判。 As can be seen from Table 8, there is no significant difference between the fruity aroma index obtained in Examples 1-2 and the fruity index sensory evaluation score, which proves the accuracy of the method for characterizing and evaluating the fruity aroma characteristics in cigarette aroma proposed by the present invention. feasibility. Moreover, in the implementation process, the subjectivity of conventional sensory evaluation methods can be avoided, and the fruity aroma style of cigarettes can be characterized and judged more objectively.
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| CN106290641A (en) * | 2016-08-11 | 2017-01-04 | 云南中烟工业有限责任公司 | A kind of quantitative forecasting technique of Medicated cigarette delicate fragrance type |
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| CN119291086A (en) * | 2024-12-11 | 2025-01-10 | 云南中烟工业有限责任公司 | An evaluation method for fruity aroma of cigarette smoke and its application |
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