乙醇含量对黄酒挥发性组分检测的影响

doi:10.3724/SP.J.1123.2022.07018

摘要/Abstract

摘要：

黄酒是风味独特的发酵酒,酒中组分复杂,且不同种类黄酒中乙醇含量差异较大。通过顶空-气相色谱法(HS-GC)测量不同乙醇含量的黄酒中挥发性组分色谱峰面积的变化,分析了乙醇引起的基质效应对不同挥发性组分定量检测的影响。在乙醇含量为10%~19% vol(酒精度)的黄酒中,16种挥发性组分(仲丁醇、正丙醇、异丁醇、正丁醇、异戊醇、β-苯乙醇、乙醛、异戊醛、苯甲醛、甲酸乙酯、乙酸乙酯、乙酸异丁酯、乙酸异戊酯、己酸乙酯、乳酸乙酯、丁二酸二乙酯)的峰面积与乙醇含量呈线性负相关。酒中乙醇含量的升高改变了其他大部分微量挥发性组分的气液平衡。乙缩醛的峰面积与乙醇含量呈线性正相关,两者在乙醇浓度变化过程中发生化学反应。甲醇、糠醛和乙酸的峰面积受乙醇含量的影响较小。色谱峰面积受乙醇含量的影响系数为-12.4%~4.9%,不同挥发性组分的蒸汽压及气液平衡受到乙醇基质效应的影响程度不同。将不同黄酒样品调整至同一酒精度后,不同样品中挥发性组分在溶液中的含量与色谱峰总面积成正比,乙醇引起的基质效应对检测结果的干扰得到有效降低。研究人员在使用基于气液平衡等原理的前处理方法开展风味组分定量检测时,应将不同黄酒样品调整至相同的酒精度,才能有效控制乙醇含量差异引起的基质效应,实现准确的定量分析。

关键词: 顶空-气相色谱法, 乙醇, 基质效应, 挥发性组分, 定量检测

Abstract:

Huangjiu (Chinese rice wine) is a traditional Chinese fermented wine with a unique flavor. The components of this wine are complex, and the ethanol content of different Huangjiu preparations varies greatly. In this study, changes in the chromatographic peak areas of the volatile components of Huangjiu samples with different ethanol contents were measured using headspace-gas chromatography (HS-GC). The influence of ethanol on the quantitative detection of different volatile components of Huangjiu at gas-liquid equilibrium was also analyzed. When the ethanol content of Huangjiu was in the range of 10%-19% vol, the peak areas of 16 volatile components (i. e., sec-butanol, n-propanol, isobutanol, n-butanol, isoamyl alcohol, β-phenyl-ethanol, acetaldehyde, isovaleraldehyde, benzaldehyde, ethyl formate, ethyl acetate, isobutyl acetate, isoamyl acetate, ethyl hexanoate, ethyl lactate, and diethyl succinate) were negatively correlated with the ethanol content. Increases in the ethanol content of the liquor changed the gas-liquid equilibrium of most other trace volatile components. In addition, only the peak area of acetal was positively correlated with ethanol content. The content of acetal in Huangjiu was affected by the alcohol content, and its decomposition reaction occurred along with the dilution process. The influence coefficient of ethanol content on the peak area of the above compounds ranged from -12.4% to 4.9%. The vapor pressure of most volatile components decreased with increasing ethanol content, and different components were affected in different ways. Compared with those of other components, the peak areas of methanol, furfural, and acetic acid were less affected by the ethanol content. These components were also affected by other factors, such as ionization and chemical reactions occurring during the dilution process. When different wine samples were adjusted to the same ethanol content, the concentration of volatile components in these samples became proportional to the total chromatographic peak area and the influence of the matrix effect of ethanol on the quantitative analysis was effectively eliminated. Thus, when researchers use pretreatment methods based on the principle of gas-liquid balance to carry out the quantitative detection of flavor components, they should adjust different rice wine samples to the same alcohol content to effectively control the matrix effect caused by differences in ethanol content and achieve accurate quantitative analysis.

Key words: headspace-gas chromatography (HS-GC), ethanol, matrix effect, volatile components, quantitative detection

中图分类号:

O658

胡健, 黄媛媛, 刘双平, 毛健. 乙醇含量对黄酒挥发性组分检测的影响[J]. 色谱, 2023, 41(5): 450-455.

HU Jian, HUANG Yuanyuan, LIU Shuangping, MAO Jian. Influence of ethanol content on the detection of volatile components in Huangjiu[J]. Chinese Journal of Chromatography, 2023, 41(5): 450-455.

图/表 6

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Sample No.	Pretreatment method
1	70 mL Huangjiu+30 mL water
2	90 mL Huangjiu+10 mL water
3	100 mL Huangjiu
4	100 mL Huangjiu+2 mL ethanol
5	100 mL Huangjiu+5 mL ethanol
6	80 mL Huangjiu+20 mL 15% ethanol aqueous solution

Sample No.	Pretreatment method
1	70 mL Huangjiu+30 mL water
2	90 mL Huangjiu+10 mL water
3	100 mL Huangjiu
4	100 mL Huangjiu+2 mL ethanol
5	100 mL Huangjiu+5 mL ethanol
6	80 mL Huangjiu+20 mL 15% ethanol aqueous solution

Sample No.	Alcohol content/ (% vol)	Density/ (g/cm³)	Dilution rate
1	10.31±0.02	1.0001±0.0002	1.442
2	13.22±0.03	1.0011±0.0002	1.120
3	14.71±0.01	1.0016±0.0001	1.000
4	16.43±0.02	0.9995±0.0002	1.016
5	18.81±0.02	0.9964±0.0002	1.045
6	14.76±0.03	0.9974±0.0004	0.802

Sample No.	Alcohol content/ (% vol)	Density/ (g/cm³)	Dilution rate
1	10.31±0.02	1.0001±0.0002	1.442
2	13.22±0.03	1.0011±0.0002	1.120
3	14.71±0.01	1.0016±0.0001	1.000
4	16.43±0.02	0.9995±0.0002	1.016
5	18.81±0.02	0.9964±0.0002	1.045
6	14.76±0.03	0.9974±0.0004	0.802

No.	Compound	R²	a	Peak area of original sample (No. 3)	Influence coefficient/%
1	acetaldehyde	0.8652	-2.9801	117.5±1.5	-2.5
2	ethyl formate	0.9450	-0.2643	9.22±0.14	-2.9
3	ethyl acetate	0.9747	-14.872	285.0±3.7	-5.2
4	acetal	0.8690	2.6619	54.0±0.9	4.9
5	methanol	0.1133	-0.0286	3.68±0.13	/
6	isovaleraldehyde	0.9767	-0.6962	10.4±0.1	-6.7
7	isobutyl acetate	0.9613	-0.0456	0.60±0.05	-7.6
8	sec-butanol	0.9582	-0.1200	1.58±0.01	-7.7
9	n-propanol	0.8529	-1.0681	26.0±0.4	-4.1
10	isobutanol	0.9667	-13.436	182.1±2.5	-7.4
11	isoamyl acetate	0.9517	-0.1566	1.52±0.03	-10.3
12	n-butanol	0.9349	-0.0498	0.67±0.02	-7.5
13	isoamyl alcohol	0.9626	-33.069	315.7±4.4	-10.5
14	ethyl hexanoate	0.8672	-0.0966	0.78±0.01	-12.4
15	ethyl lactate	0.8417	-0.6795	14.8±0.7	-4.6
16	acetic acid	0.0193	0.0151	3.27±0.21	/
17	furfural	0.1447	-0.0805	1.06±0.04	/
18	benzaldehyde	0.9539	-0.1215	1.15±0.03	-10.6
19	diethyl succinate	0.9139	-0.1071	0.93±0.01	-11.5
20	β-phenylethanol	0.8366	-0.3499	4.62±0.31	-7.6