离子色谱指纹图谱分析在烟用香精香料品质评价中的应用

doi:10.3724/SP.J.1123.2023.11008

摘要/Abstract

摘要：

为保证烟用香精香料品质的一致性,采用离子色谱法对烟用香精香料样品中的9种有机酸及7种无机阴离子进行分析。1.0 g样品中加入10 mL去离子水,振荡萃取30 min后,水相溶液用0.45 μm微孔滤膜过滤,滤液进一步采用RP前处理柱除去基质,经离子色谱仪分离测定。采用Dionex IonPac AS11-HC阴离子交换柱及淋洗液梯度洗脱,9种有机酸和7种常规无机阴离子标准工作溶液的保留时间和峰面积日内精密度(RSD)分别为0.01%~0.69%和1.34%~2.98%,日间RSD分别为0.03%~0.68%和3.54%~5.16%。同时对烟用香精香料标准样品A~D (各5个批次)中有机酸和无机酸的保留时间和峰面积RSD进行考察,得到的保留时间和峰面积日内RSD分别为0.01%~0.71%和2.39%~3.22%,日间RSD分别0.05%~0.81%和3.61%~6.02%。建立了4种烟用香精香料(各5个批次)的指纹谱图库,并采用系统聚类分析和相似度分析法对其他生产厂家样品进行品质评价。结果表明,聚类分析法能有效地从不同生产厂家的产品中筛选出与标准样品质量最相近的样品;实际样品AY3、BY2、CY2及DY1与香精香料标准品性质最接近,品质较好。相似度分析可以对不同生产厂家的产品质量进行更加具体、量化的评价,实际样品AY3、BY2、CY2及DY1与香精香料标准品的化学成分相似度值均大于97.7%,符合相似度评价要求。相较于超声辅助液液萃取-气相色谱法,对于个别特殊样品,离子色谱法能更有效地区分香精香料样品间的品质差异。

关键词: 离子色谱法, 烟用香精香料, 色谱指纹图谱, 聚类分析, 相似度分析

Abstract:

Tobacco flavor, an important tobacco additive, is an essential raw material in cigarette production that can effectively improve the quality of tobacco products, add aroma and taste, and increase the suction flavor. The quality consistency of tobacco flavors affects the quality stability of branded cigarettes. Therefore, the quality control of tobacco flavors is a major concern for cigarette and flavor manufacturers. Physical and chemical indices, odor similarity, and sensory efficacy are employed to evaluate the quality of tobacco flavors, and the analysis of chemical components in tobacco flavors is usually conducted using gas chromatography (GC) and high performance liquid chromatography (HPLC). However, because the composition of tobacco flavors is complex, their quality cannot be fully reflected using a single component or combination of components. Therefore, establishing an objective analytical method for the quality control of tobacco flavors is of extreme importance. Chromatographic fingerprint analysis is routinely used for the discriminative analysis of tobacco flavors. Chromatographic fingerprints refer to the general characteristics of the concentration profiles of different chemical compounds. In the daily procurement process, fingerprints established by GC and HPLC are effective for the evaluation and identification of tobacco flavors. However, given continuous improvements in aroma-imitation technology, some flavors with high similarity cannot be directly distinguished using existing methods.

In this study, a method for the determination of organic acids and inorganic anions in tobacco flavors based on ion chromatography (IC) was developed to ensure the quality consistency of tobacco flavors. A 1.0 g sample of tobacco flavors and 10 mL of deionized water were mixed and vibrated for 30 min. The aqueous sample solution was passed through a 0.45 μm membrane filter and RP pretreatment column in succession to eliminate interferences and then subjected to IC. Standard solutions containing nine organic acids and seven inorganic anions were used to identify the anions in the tobacco flavors, and satisfactory reproducibility was obtained. The relative standard deviations (RSDs) for retention times and peak areas were <0.71% and <6.02%, respectively. The chromatographic fingerprints of four types of tobacco flavors (samples A-D) from five different batches were obtained. Nine tobacco flavor samples from different manufacturers (samples AY1-AY3, BY1-BY2, CY1-CY2, DY1-DY2) were also analyzed to obtain their chromatographic fingerprints. Hierarchical cluster and similarity analyses were used to evaluate the quality of tobacco flavors from different manufacturers. Hierarchical clustering refers to the process of subdividing a group of samples into clusters that exhibit a high degree of intracluster similarity and intercluster dissimilarity. The dendrograms obtained using SPSS 12.0 indicated good quality consistency among the samples in different batches. Samples AY3, BY2, CY2, and DY1 clustered with the batches of standard tobacco flavors. Therefore, hierarchical cluster analysis can effectively distinguish the quality of products from different manufacturers. The Similarity Evaluation System for Chromatographic Fingerprint of Traditional Chinese Medicine (version 2.0) was used to evaluate the similarity between the standard tobacco flavors and products from different manufacturers. Among the samples analyzed, samples AY3, BY2, CY2, and DY1 showed the highest similarity values (>97.7%), which was consistent with the results of the hierarchical cluster analysis. This finding indicates that IC combined with chromatographic fingerprint analysis could accurately determine the quality of tobacco flavors. GC combined with ultrasonic-assisted liquid-liquid extraction was also used to analyze the tobacco flavors and verify the accuracy of the proposed method. Compared with GC coupled with ultrasonic-assisted liquid-liquid extraction, IC demonstrated more significant quality differences among certain tobacco flavors.

Key words: ion chromatography (IC), tobacco flavors, chromatographic fingerprint, hierarchical cluster analysis, similarity analysis

中图分类号:

O658

许高燕, 何歆滢, 张丽娜, 刘崇盛, 高阳, 黄忠平, 刘会君, 吴兆明, 章瑞潮, 施宏. 离子色谱指纹图谱分析在烟用香精香料品质评价中的应用[J]. 色谱, 2024, 42(8): 805-811.

XU Gaoyan, HE Xinying, ZHANG Lina, LIU Chongsheng, GAO Yang, HUANG Zhongping, LIU Huijun, WU Zhaoming, ZHANG Ruichao, SHI Hong. Application of ion chromatographic fingerprint analysis for quality evaluation of tobacco flavors[J]. Chinese Journal of Chromatography, 2024, 42(8): 805-811.

图/表 4

图1 标准混合溶液的色谱图及4种香精香料的色谱指纹图谱

Fig. 1 Chromatograms of standard solution and chro- matographic fingerprints of the four tobacco flavors with different batches 1. lactic acid; 2. acetic acid; 3. fluoride; 4. formic acid; 5. propionic acid; 6. chloride; 7. nitrite; 8. bromide; 9. nitrate; 10. malic acid; 11. tartaric acid; 12. malonic acid; 13. sulfate; 14. fumaric acid; 15. phosphate; 16. citric acid.

图2 烟用香精香料的系统聚类树系图

Fig. 2 Hierarchical cluster analysis of tobacco flavors

表1 不同生产厂家的烟用香精香料样品的相似度分析

Table 1 Similarity evaluation of tobacco flavors from different manufacturers

Sample name	Similarity with the tobacco flavor standards/%
AY1	43.7
AY2	39.1
AY3	97.9
BY1	76.6
BY2	98.8
CY1	91.9
CY2	99.9
DY1	99.1
DY2	89.9

图3 B类型烟用香精香料样品的(a)气相色谱图和(b)离子色谱图

Fig. 3 (a) Gas chromatograms and (b) ion chromatograms for the determination of tobacco flavor B samples Peak Nos. 1-16 were the same as those in Fig. 1.

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