指纹图谱结合化学模式识别评价特定品牌酱香型白酒品质独特性与批次稳定性研究

王丽; 卢君; 唐平; 山其木格; 毕荣宇; 王凡; 郭莹; 李长文

doi:10.13386/j.issn1002-0306.2022040146

指纹图谱结合化学模式识别评价特定品牌酱香型白酒品质独特性与批次稳定性研究

doi: 10.13386/j.issn1002-0306.2022040146

王丽^{1, 2,},
卢君^{1, 2,*, ,},
唐平^{1, 2},
山其木格^{1, 2},
毕荣宇^{1, 2},
王凡^{1, 2},
郭莹^{1, 2},
李长文¹

1.
贵州国台酒业集团股份有限公司，贵州仁怀 564501
2.
天士力控股集团有限公司研究院，天津 300410

基金项目: 贵州省科技成果应用及产业化计划项目（黔科合成果[2020]2Y045）；贵州省仁怀市科技计划项目（仁科支撑[2020]04号）；遵义市科技计划项目（遵市科合支撑 GY[2021]40号）。

详细信息

作者简介:
王丽（1987−），女，博士，副高级工程师，研究方向：酒类风味化学，E-mail：liwangdz@sina.cn

通讯作者:
卢君（1985−），男，博士，正高级工程师，研究方向：酒类发酵技术和质量控制，E-mail：lujun951@tasly.com

中图分类号: TS261.7
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出版历程
- 收稿日期: 2022-04-14
- 刊出日期: 2023-05-01

Evaluation of Quality Uniqueness and Batch Stability of Maotai-flavor Baijiu of Specific Brand by Fingerprint and Chemical Pattern Recognition

WANG Li^{1, 2
,},
LU Jun^{1, 2,*
, ,},
TANG Ping^{1, 2},
SHAN Qimuge^{1, 2},
BI Rongyu^{1, 2},
WANG Fan^{1, 2},
GUO Ying^{1, 2},
LI Changwen¹

1.
Guizhou Guotai Liquor Group Co., Ltd., Renhuai 564501, China
2.
Tasly Research Academy, Tianjin 300410, China

摘要

摘要: 为建立一种特定品牌酱香型白酒品质独特性及批次稳定性的评价方法。采用气相色谱-质谱联用结合“中药色谱指纹图谱评价系统”，构建特定品牌酱香型白酒指纹图谱，结合相似度与化学模式识别分析（层次聚类、主成分分析）实现对特定品牌酱香型白酒品质独特性与批次稳定性的综合评价。结果表明：以指纹图谱相似度大于0.99作为特定品牌酱香型白酒品质独特性及批次稳定性的评价标准，可将特定品牌酱香型白酒与其他不同品牌酱香型白酒有效区分；化学模式识别均显示特定品牌酱香型白酒与其他不同品牌酱香型白酒明显分类；可见指纹图谱结合化学模式识别可有效评价特定品牌酱香型白酒的批次稳定性及品质独特性。主成分分析发现特定品牌酱香型白酒与其他品牌酱香型白酒差异物质为17种，包括己酸、己酸乙酯、正己醇、乙酸、苯乙酸乙酯、2-羟基丙酸乙酯、十六烷酸乙酯、丁酸、3-甲基丁醇、2-甲基丙醇、乙酸正丙酯、正丙醇、2-丁醇，2-甲基丙酸乙酯、3-甲基丁酸乙酯、丙酸乙酯、正丁醇，是特定品牌酱香型白酒品质独特性的内在体现。本研究为特定品牌酱香型白酒的质量控制提供了一定的理论依据和技术支撑。
- 酱香型白酒 /
- 气相色谱-质谱联用 /
- 指纹图谱 /
- 化学模式识别 /
- 品质独特性 /
- 批次稳定性
Abstract: This study aimed to establish an evaluation method for quality uniqueness and batch stability of Maotai-flavor Baijiu of specific brand. In this study, Gas chromatography-mass spectrometry (GC-MS) and similarity evaluation system for chromatographic fingerprints of TCM were used to establish a fingerprint of Maotai-flavor Baijiu of specific brand. As well as, comprehensive evaluation quality uniqueness and batch stability of Maotai-flavor Baijiu of specific brand was conducted based on similarity evaluation and chemical pattern recognition (hierarchical clustering and principal component analysis). The results showed that evaluation standard for quality uniqueness and batch stability of Maotai-flavor Baijiu of specific brand was fingerprint similarity greater than 0.99, which could effectively distinguish Maotai-flavor Baijiu of specific brand from other brands. The results of chemical pattern recognition showed that Maotai-flavor Baijiu of specific brand and other brands of Maotai-flavor Baijiu were obviously classified. Thus, the quality uniqueness and batch stability of Maotai-flavor Baijiu of specific brands could be effectively evaluated by the fingerprint similarity and chemical pattern recognition. 17 substances were found by principal component analysis, which caused the difference between Maotai-flavor Baijiu of specific brand and other brands. Hexanoic acid, hexanoic acid, ethyl ester, 1-hexanol, acetic acid, benzeneacetic acid, ethyl ester, propanoic acid, 2-hydroxy-, ethyl ester, hexadecanoic acid, ethyl ester, butanoic acid, 1-butanol, 3-methyl-, 1-propanol, 2-methyl-, n-propyl acetate, 1-propanol, 2-butanol , propanoic acid, 2-methyl-, ethyl ester, butanoic acid, 3-methyl-, ethyl ester, propanoic acid, ethyl ester, 1-butanol were included. These substances were the inherent embodiment of Maotai-flavor Baijiu of specific brand uniqueness. This study provides theoretical basis and technical support for the quality control of Maotai-flavor Baijiu of specific brand.
- Maotai-flavor Baijiu /
- gas chromatography-mass spectrometry /
- fingerprint /
- chemical pattern recognition /
- quality uniqueness /
- batch stability

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图 1 特定品牌酱香型白酒GC-MS谱图及对照指纹谱

Figure 1. GC-MS chromatogram of Maotai-flavor Baijiu of specific brand and control fingerprint

下载: 全尺寸图片幻灯片

图 2 不同白酒的聚类分析树状图

Figure 2. Cluster analysis dendrogram of different Baijiu

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图 3 基于GC-MS的主成分分析

Figure 3. PCA based on GC-MS

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图 4 主成分分析载荷图

Figure 4. Loading plot of PCA

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表 1 GC-MS方法学考察

Table 1. GC-MS methodology investigation

编号	保留时间（min）	物质名称	精密度		稳定性		重复性
编号	保留时间（min）	物质名称	相对峰面积RSD（%）	相对保留时间RSD（%）	相对峰面积RSD（%）	相对保留时间RSD（%）	相对峰面积RSD（%）	相对保留时间RSD（%）
1	6.98	丙酸乙酯^a	1.6013	0.1016	1.8007	0.1321	1.7328	0.1996
2	7.12	2-甲基丙酸乙酯^a	1.1927	0.1180	2.0095	0.1209	1.7440	0.1497
3	7.35	乙酸丙酯^a	2.7918	0.0748	2.2246	0.0817	2.6925	0.0966
4	8.61	2-丁醇^a	1.4499	0.0638	3.9036	0.0595	0.9538	0.0824
5	9.07	正丙醇^a	1.1517	0.0497	1.7357	0.0567	1.4546	0.0393
6	9.50	2-甲基丁酸乙酯	1.4149	0.0474	1.4888	0.0539	0.7444	0.0375
7	10.07	3-甲基丁酸乙酯^a	0.7283	0.0448	0.9569	0.0305	1.2904	0.0354
8	10.73	2-甲基丙醇^a	1.6455	0.0000	2.2216	0.0143	1.6166	0.0433
9	11.97	正丁醇^a	1.6269	0.0355	1.7015	0.0398	1.4556	0.0424
10	12.42	戊酸乙酯^a	0.5863	0.0000	0.8065	0.0220	0.7495	0.0420
11	14.25	2-庚酮	1.4187	0.0386	1.6813	0.0173	2.6086	0.0000
12	15.07	3-甲基丁醇^a	1.0328	0.0000	1.7355	0.0143	1.6934	0.0495
13	16.14	己酸乙酯^a	0.6308	0.0278	1.2289	0.0311	1.5504	0.0220
14	16.67	正戊醇	0.6319	0.0330	1.7242	0.0127	1.3126	0.0213
15	20.21	2-羟基丙酸乙酯^a	0.7734	0.0272	2.8189	0.0143	1.1350	0.0265
16	20.31	正己醇^a	0.5315	0.0000	1.1683	0.0078	1.0576	0.0256
17	22.13	2-羟基丁酸乙酯	1.9304	0.0248	1.7532	0.0230	1.7235	0.0160
18	22.2	三甲基吡嗪	5.0642	0.0000	4.6352	0.0224	4.3043	0.0159
19	22.92	辛酸乙酯	0.3559	0.0000	1.8260	0.0211	1.6576	0.0203
20	23.62	乙酸^a	1.3539	0.0000	1.6795	0.0048	3.6102	0.0150
21	24.26	糠醛^a	0.6800	0.0000	1.4900	0.0143	1.0800	0.0214
22	25.40	乙酰呋喃	3.6194	0.0000	3.5738	0.0205	2.9430	0.0140
23	25.97	苯甲醛	0.8088	0.0000	1.7522	0.0030	0.8875	0.0179
24	28.33	丁酸^a	1.1094	0.0000	0.5792	0.0016	1.0254	0.0000
25	29.55	丁二酸二乙酯	0.9454	0.0000	0.8255	0.0180	1.0435	0.0157
26	30.58	（2,2-二乙氧基乙基）-苯	2.7736	0.0179	0.8405	0.0004	3.0769	0.0000
27	30.98	戊酸	0.7996	0.0000	0.8970	0.0176	1.3099	0.0000
28	32.32	苯乙酸乙酯^a	1.3121	0.0000	1.5834	0.0004	1.3071	0.0000
29	33.40	己酸^a	0.9011	0.0134	1.1881	0.0170	1.3478	0.0160
30	34.53	苯丙酸乙酯	2.7303	0.0159	1.5826	0.0013	2.5115	0.0000
31	35.13	苯乙醇^a	1.1585	0.0000	1.5712	0.0163	0.9476	0.0101
32	41.44	棕榈酸乙酯^a	5.1705	0.0111	5.6147	0.0107	8.5698	3.5145
注：a代表特征成分，表2同。

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表 2 特定品牌酱香型白酒 GC-MS 共有成分的总峰面积占比

Table 2. Ratio of total peak area of common substances of Maotai-flavor Baijiu of specific brand based on GC-MS

编号	保留时间（min）	物质名称	总峰面积占比（%）
编号	保留时间（min）	物质名称	S1	S2	S3	S4	S5	S6	S7	S8	S9	S10	S11	S12
1	6.98	丙酸乙酯^a	3.950±0.0141	4.495±0.0354	3.895±0.0071	3.220±0.0141	2.595±0.0212	2.735±0.0071	2.800±0.0424	2.660±0.0283	2.505±0.0071	2.220±0.0141	2.335±0.0071	2.345±0.0071
2	7.12	2-甲基丙酸乙酯^a	1.395±0.0071	1.355±0.0071	1.375±0.0071	1.335±0.0071	1.015±0.0071	1.095±0.0071	1.000±0.0141	1.115±0.0354	1.210±0.0000	1.040±0.0141	1.050±0.0000	1.045±0.0071
3	7.35	乙酸丙酯^a	1.010±0.0000	0.9300±0.0000	1.000±0.0000	0.4300±0.000	0.6800±0.0000	0.7900±0.0000	1.375±0.0071	1.375±0.0212	0.4750±0.0071	0.6350±0.0071	0.6100±0.0000	0.6350±0.0354
4	8.61	2-丁醇^a	1.025±0.0071	0.8800±0.0000	1.020±0.0000	0.6350±0.0071	0.9100±0.0141	0.9050±0.0071	1.000±0.0000	0.9300±0.0141	0.6600±0.0000	1.305±0.0071	1.245±0.0212	1.235±0.0071
5	9.07	正丙醇^a	15.02±0.1768	14.58±0.0354	15.06±0.1061	14.56±0.3677	12.20±0.0424	12.70±0.0566	15.33±0.0919	14.22±0.2192	9.960±0.0000	14.37±0.0354	11.97±0.0424	13.825±0.0636
6	9.50	2-甲基丁酸乙酯	0.3500±0.0000	0.3600±0.0000	0.3450±0.0071	0.3300±0.0000	0.2600±0.000	0.2650±0.0071	0.2500±0.0000	0.2350±0.0071	0.2750±0.0071	0.3150±0.0071	0.2850±0.0071	0.2750±0.0071
7	10.07	3-甲基丁酸乙酯^a	0.9650±0.0071	1.005±0.0071	0.9400±0.000	0.9750±0.0071	0.7650±0.0071	0.7800±0.0000	0.700±0.0000	0.6900±0.0141	0.8700±0.0000	0.9400±0.0141	0.8400±0.0000	0.8350±0.0071
8	10.73	2-甲基丙醇^a	2.935±0.0212	2.865±0.0071	2.925±0.0071	3.140±0.0141	3.000±0.0424	3.035±0.0071	2.980±0.0141	2.760±0.0424	2.835±0.0071	3.010±0.0283	2.940±0.0000	2.905±0.0495
9	11.97	正丁醇^a	1.480±0.0141	1.425±0.0071	1.465±0.0071	1.890±0.0141	2.520±0.0283	2.525±0.0071	2.335±0.0071	2.190±0.0283	2.095±0.0071	1.875±0.0071	2.240±0.0000	2.385±0.2051
10	12.42	戊酸乙酯^a	1.415±0.0071	1.350±0.0000	1.380±0.0000	1.150±0.0000	1.035±0.0071	1.000±0.0000	0.9750±0.0071	0.9750±0.0071	1.055±0.0071	0.9950±0.0071	1.025±0.0071	1.030±0.0141
11	14.25	2-庚酮	0.0300±0.0000	0.0300±0.0000	0.0300±0.0000	0.0200±0.0000	0.0200±0.0000	0.0200±0.0000	0.0200±0.0000	0.0200±0.0000	0.0250±0.0071	0.0300±0.0000	0.0500±0.0000	0.0500±0.0000
12	15.07	3-甲基丁醇^a	16.23±0.0071	15.41±0.0000	15.92±0.0212	15.68±0.0212	14.47±0.0141	14.16±0.0495	14.09±0.0283	13.06±0.1414	14.30±0.0424	15.35±0.0071	15.58±0.099	15.16±0.502
13	16.14	己酸乙酯^a	4.410±0.0424	4.020±0.0283	4.322±0.0424	4.195±0.0071	4.485±0.0071	4.270±0.0283	4.050±0.0283	4.130±0.0141	4.240±0.0000	3.535±0.0212	3.985±0.0354	3.650±0.4384
14	16.67	正戊醇	0.3650±0.0071	0.3550±0.0071	0.3552±0.0071	0.3650±0.0071	0.3800±0.0000	0.3600±0.0000	0.3700±0.0000	0.3450±0.0071	0.365±0.0071	0.3250±0.0071	0.3650±0.0071	0.3550±0.0212
15	20.21	2-羟基丙酸乙酯^a	16.88±0.1061	17.25±0.0495	16.52±0.0000	18.54±0.0283	18.85±0.0354	19.13±0.0707	18.41±0.0636	16.66±0.0919	17.50±0.1273	18.84±0.0354	18.34±0.0778	19.04±0.9192
16	20.31	正己醇^a	1.070±0.0000	1.060±0.0000	1.020±0.0000	1.215±0.0071	1.410±0.0141	1.350±0.0141	1.310±0.0000	1.235±0.0212	1.285±0.0071	1.065±0.0071	1.190±0.0000	1.100±0.1273
17	22.13	2-羟基丁酸乙酯	0.0300±0.0000	0.0200±0.0000	0.0300±0.0000	0.0250±0.0071	0.0200±0.0000	0.0200±0.0000	0.0200±0.0000	0.0200±0.0000	0.0200±0.0000	0.0300±0.0000	0.0200±0.0000	0.0215±0.0021
18	22.2	三甲基吡嗪	0.1850±0.0071	0.1550±0.0071	0.1800±0.0000	0.1450±0.0071	0.1200±0.0141	0.1000±0.0000	0.1000±0.0000	0.0900±0.0000	0.1250±0.0071	0.1350±0.0071	0.1400±0.0000	0.1300±0.0141
19	22.92	辛酸乙酯	0.2250±0.0071	0.2400±0.0000	0.2250±0.0071	0.2000±0.0000	0.1800±0.0000	0.1700±0.0000	0.1600±0.0000	0.1750±0.0071	0.2300±0.0000	0.2550±0.0071	0.3300±0.0000	0.3350±0.0071
20	23.62	乙酸^a	1.255±0.0495	1.265±0.0071	1.290±0.0424	1.355±0.0071	1.245±0.0354	1.395±0.0071	1.335±0.0071	1.260±0.0000	1.310±0.0141	1.220±0.0283	1.490±0.0141	1.580±0.1131
21	24.26	糠醛^a	10.59±0.0141	10.74±0.0000	10.19±0.0354	13.18±0.1273	14.10±0.0778	14.29±0.0566	12.51±0.0849	11.75±0.1697	11.24±0.0849	9.810±0.0283	9.365±0.0495	9.035±0.5162
22	25.40	乙酰基呋喃	0.1300±0.0000	0.1200±0.0000	0.1200±0.0000	0.1350±0.0071	0.1400±0.0000	0.1450±0.0071	0.1400±0.000	0.1300±0.0000	0.1300±0.0000	0.1300±0.0000	0.1300±0.0000	0.1250±0.0071
23	25.97	苯甲醛	0.4750±0.0071	0.4850±0.0071	0.4600±0.0000	0.4800±0.0000	0.5100±0.0000	0.500±0.0000	0.4400±0.0000	0.4150±0.0071	0.4700±0.0000	0.4150±0.0071	0.4050±0.0071	0.4000±0.0141
24	28.33	丁酸^a	1.150±0.0141	1.115±0.0071	1.130±0.0000	1.115±0.0071	1.085±0.0071	1.070±0.0000	1.030±0.0000	0.9500±0.0141	1.055±0.0071	1.050±0.0000	1.190±0.0141	1.270±0.0990
25	29.55	丁二酸二乙酯	0.3900±0.0000	0.3500±0.0000	0.3750±0.0071	0.3600±0.0000	0.2800±0.0000	0.2700±0.0000	0.2600±0.0000	0.2300±0.0000	0.2700±0.0000	0.2600±0.0000	0.2300±0.0000	0.2250±0.0071
26	30.58	（2,2-二乙氧基乙基）-苯	0.0500±0.0000	0.0300±0.0000	0.0500±0.0000	0.0700±0.0000	0.0750±0.0071	0.0800±0.0000	0.0950±0.0071	0.1200±0.0000	0.0850±0.0071	0.0600±0.0000	0.0800±0.0000	0.0750±0.0071
27	30.98	戊酸	0.4200±0.0000	0.3900±0.0000	0.4100±0.0000	0.3400±0.0000	0.3200±0.0000	0.295±0.0071	0.3000±0.0000	0.2750±0.0071	0.3100±0.000	0.2900±0.0000	0.3400±0.0000	0.3500±0.0141
28	32.32	苯乙酸乙酯^a	0.5900±0.0141	0.5400±0.0000	0.5750±0.0071	0.5450±0.0071	0.4650±0.0071	0.4400±0.0000	0.4050±0.0071	0.3850±0.0071	0.4450±0.0071	0.4500±0.0000	0.3950±0.0071	0.3850±0.0071
29	33.40	己酸^a	2.030±0.0000	1.805±0.0071	1.955±0.0071	1.920±0.0000	2.080±0.0141	1.925±0.0071	1.850±0.0141	1.770±0.0283	1.850±0.0000	1.480±0.0000	1.895±0.0071	1.805±0.1344
30	34.53	苯丙酸乙酯	0.0600±0.0000	0.0550±0.0071	0.0550±0.0071	0.05±0.0000	0.0400±0.0000	0.0400±0.0000	0.0400±0.0000	0.0400±0.0000	0.0400±0.0000	0.0500±0.0000	0.0300±0.0000	0.0300±0.0000
31	35.13	苯乙醇^a	1.560±0.0000	1.520±0.0000	1.500±0.0000	1.495±0.0071	1.355±0.0071	1.300±0.0000	1.250±0.0000	1.155±0.0212	1.390±0.0141	1.380±0.0141	1.790±0.0000	1.720±0.0990
32	41.44	十六烷酸乙酯^a	0.8250±0.0212	1.040±0.0000	0.8750±0.0071	1.025±0.0071	0.8400±0.0141	0.7650±0.0071	0.9150±0.0071	0.9100±0.0141	0.9700±0.0141	0.9550±0.0071	0.9050±0.0212	0.9400±0.0141

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表 3 基于特定品牌酱香型白酒GC-MS 指纹图谱相似度计算结果

Table 3. Similarity results based on GC-MS fingerprint of Maotai-flavor Baijiu of specific brand

样品编号	相似度	样品编号	相似度	样品编号	相似度
S1	0.997	S12	0.997	LJ2	0.964
S2	0.997	LJ4	0.922	LJ3	0.943
S3	0.997	DYT1	0.951	LJ5	0.934
S4	0.996	DYT2	0.947	MT1	0.946
S5	0.998	DYT3	0.956	MT2	0.933
S6	0.998	DYT4	0.954	MT3	0.901
S7	0.998	JS1	0.926	MT4	0.907
S8	0.998	JS2	0.938	XJ1	0.975
S9	0.998	JS3	0.952	XJ2	0.971
S10	0.998	JS4	0.937	XJ3	0.973
S11	0.998	LJ1	0.928	XJ4	0.975

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表 4 相似度方差分析

Table 4. Variance analysis of similarity

品牌	相似度
S	0.9975^a
XJ	0.9735^b
DYT	0.952^c
JS	0.93825^c
LJ	0.9382^c
MT	0.92175^d
注：同列不同小写字母表示差异显著（P<0.05）。

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表 5 特定品牌酱香型白酒 GC-MS 特征成分的相对含量

Table 5. Relative content of characteristic substances of Maotai-flavor Baijiu of specific brand based on GC-MS

编号	保留时间（min）	物质名称	相对含量（g/L）
编号	保留时间（min）	物质名称	S1	S2	S3	S4	S5	S6	S7	S8	S9	S10	S11	S12
1	6.98	丙酸乙酯	0.0576±0.0007	0.0644±0.0007	0.0582±0.0006	0.0464±0.0001	0.0407±0.0001	0.0428±0.0001	0.0457±0.0008	0.0454±0.0005	0.0393±0.0007	0.3862±0.0013	0.0391±0.0002	0.0352±0.0057
2	7.12	2-甲基丙酸乙酯	0.0203±0.0003	0.0194±0.0000	0.0206±0.0000	0.0193±0.0002	0.0159±0.0002	0.0171±0.0001	0.0164±0.0003	0.0183±0.0017	0.0186±0.001	0.0177±0.0001	0.0175±0.0001	0.0152±0.0034
3	7.35	乙酸丙酯	0.0147±0.0002	0.0133±0.0001	0.015±0.0002	0.0062±0.0001	0.0106±0.0001	0.0123±0.0001	0.0224±0.0002	0.0235±0.0004	0.0074±0.0002	0.0104±0.0002	0.0102±0.0000	0.0099±0.0003
4	8.61	2-丁醇	0.0149±0.0002	0.0126±0.0001	0.0153±0.0002	0.0091±0.0002	0.0143±0.0003	0.0141±0.0002	0.0163±0.0000	0.0162±0.0004	0.0105±0.0001	0.0217±0.0008	0.0209±0.0003	0.0202±0.0006
5	9.07	正丙醇	0.2191±0.0044	0.2089±0.0011	0.2252±0.0039	0.1546±0.0014	0.1913±0.0019	0.1983±0.0009	0.2499±0.0011	0.2462±0.0042	0.1576±0.0001	0.2385±0.0084	0.2002±0.0001	0.202±0.0027
6	10.07	3-甲基丁酸乙酯	0.0141±0.0002	0.0144±0.0001	0.0141±0.0001	0.014±0.0001	0.012±0.0000	0.0122±0.0000	0.0114±0.0001	0.0117±0.0004	0.0135±0.0005	0.0156±0.0004	0.014±0.0001	0.0124±0.0023
7	10.73	2-甲基丙醇	0.0428±0.0007	0.041±0.0000	0.0438±0.0004	0.0452±0.0003	0.047±0.0009	0.0474±0.0001	0.0486±0.0002	0.0478±0.0008	0.045±0.0004	0.05±0.0021	0.0491±0.0001	0.0458±0.0047
8	11.97	正丁醇	0.0216±0.0004	0.0204±0.0002	0.0219±0.0003	0.0272±0.0002	0.0396±0.0007	0.0394±0.0002	0.0381±0.0000	0.0378±0.0005	0.0334±0.0005	0.0312±0.0009	0.0374±0.0000	0.0375±0.0000
9	12.42	戊酸乙酯	0.0206±0.0004	0.0193±0.0001	0.0207±0.0002	0.0166±0.0001	0.0163±0.0000	0.0156±0.0001	0.0159±0.0001	0.0164±0.0005	0.0163±0.0006	0.0165±0.0004	0.0172±0.0001	0.0254±0.0117
10	15.07	3-甲基丁醇	0.2368±0.0021	0.2209±0.0006	0.238±0.0022	0.226±0.0007	0.2269±0.0013	0.2211±0.0008	0.2297±0.0009	0.2259±0.0032	0.2281±0.003	0.2547±0.0083	0.2605±0.0008	0.2395±0.0289
11	16.14	己酸乙酯	0.0643±0.0012	0.0576±0.0005	0.0646±0.0001	0.0605±0.0000	0.0704±0.0003	0.0667±0.0004	0.066±0.0007	0.0694±0.0028	0.0654±0.003	0.0586±0.0015	0.0666±0.0003	0.0579±0.012
12	20.21	2-羟基丙酸乙酯	0.2462±0.0036	0.2472±0.0015	0.2471±0.0026	0.2673±0.0000	0.2955±0.0015	0.2988±0.0009	0.3001±0.0004	0.2897±0.0066	0.282±0.009	0.3126±0.0095	0.3065±0.0023	0.2997±0.0119
13	20.31	正己醇	0.0156±0.0002	0.0152±0.0000	0.0153±0.0002	0.0175±0.0001	0.0221±0.0000	0.0211±0.0002	0.0214±0.0000	0.0212±0.0002	0.0203±0.0001	0.0177±0.0004	0.02±0.0001	0.0175±0.0036
14	23.62	乙酸	0.0183±0.0009	0.0182±0.0002	0.0193±0.0008	0.0195±0.0001	0.0196±0.0004	0.0217±0.0001	0.0218±0.0001	0.0217±0.0000	0.0206±0.0003	0.0203±0.0011	0.0249±0.0003	0.0248±0.0004
15	24.26	糠醛	0.1545±0.0014	0.154±0.0004	0.1523±0.0011	0.19±0.0015	0.221±0.0002	0.2232±0.0008	0.204±0.0017	0.2022±0.0019	0.1787±0.0017	0.1628±0.0047	0.1566±0.0013	0.1429±0.0206
16	28.33	丁酸	0.0168±0.0004	0.016±0.0001	0.0169±0.0002	0.0161±0.0001	0.017±0.0001	0.0167±0.0000	0.0168±0.0000	0.0164±0.0001	0.0167±0.0001	0.0174±0.0006	0.0199±0.0004	0.0209±0.0012
17	32.32	苯乙酸乙酯	0.0086±0.0002	0.0077±0.0000	0.0086±0.0000	0.0079±0.0001	0.0073±0.0001	0.0069±0.0000	0.0067±0.0001	0.0066±0.0001	0.0069±0.0002	0.0075±0.0003	0.0066±0.0000	0.0061±0.0007
18	33.40	己酸	0.0296±0.0003	0.0259±0.0002	0.0292±0.0004	0.0277±0.0000	0.0326±0.0000	0.0301±0.0000	0.0302±0.0001	0.0303±0.0003	0.0292±0.0001	0.0246±0.0007	0.0317±0.0002	0.0286±0.0045
19	35.13	苯乙醇	0.0227±0.0002	0.0218±0.0001	0.0224±0.0002	0.0215±0.0001	0.0212±0.0002	0.0203±0.0001	0.0203±0.0000	0.0199±0.0002	0.0221±0.0002	0.0229±0.0005	0.0299±0.0000	0.0255±0.0062
20	41.44	十六烷酸乙酯	0.012±0.0004	0.0149±0.0001	0.0131±0.0001	0.0148±0.0001	0.0131±0.0003	0.0119±0.0001	0.0149±0.0000	0.005±0.0084	0.0049±0.0079	0.0006±0.0000	0.0579±0.0006	0.0517±0.0093

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表 6 主成分总方差解释

Table 6. Principal component total variance explained

主成分	方差贡献率	方差累计贡献率	特征值
1	0.30	0.30	5.95
2	0.25	0.55	5.07
3	0.14	0.69	2.80
4	0.10	0.79	1.96
5	0.07	0.86	1.35

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表 7 主成分得分系数矩阵

Table 7. Principal component score coefficient matrix

特征物质	主成分1	主成分2	主成分3	主成分4	主成分5
丙酸乙酯	−0.15	0.19	0.45	0.42	−0.52
2-甲基丙酸乙酯	0.62	−0.12	0.15	0.72	−0.16
乙酸丙酯	0.48	0.08	0.76	−0.20	0.12
2-丁醇	−0.16	−0.12	0.80	−0.14	0.44
正丙醇	0.30	0.41	0.79	0.07	0.20
3-甲基丁酸乙酯	0.16	−0.53	0.03	0.72	0.09
2-甲基丙醇	0.29	−0.73	−0.36	0.19	0.29
戊酸乙酯	−0.62	0.58	0.04	0.38	−0.16
正丁醇	0.43	0.55	−0.39	0.06	0.54
3-甲基丁醇	−0.23	−0.85	−0.18	0.16	0.09
己酸乙酯	−0.88	0.31	−0.07	0.26	0.10
2-羟基丙酸乙酯	0.52	0.75	−0.20	0.05	0.11
正己醇	−0.86	0.12	−0.18	0.23	0.31
乙酸	0.86	0.17	0.02	0.30	0.13
糠醛	0.59	0.30	−0.50	−0.07	0.06
丁酸	0.21	0.78	−0.19	0.26	0.05
苯乙酸乙酯	0.76	−0.26	−0.16	−0.09	−0.36
己酸	−0.87	0.38	−0.05	0.21	0.11
苯乙醇	0.25	−0.60	0.18	0.33	0.31
十六烷酸乙酯	0.39	0.84	0.00	0.12	−0.01

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表 8 主成分得分、综合得分及排名

Table 8. Principal component scores, comprehensive scores and rankings

编号	主成分1	主成分2	主成分3	主成分4	主成分5	综合得分	排名
S9	7.33	7.93	0.11	7.14	8.31	5.42	1
S4	7.20	7.33	−1.09	8.06	7.72	5.12	2
S7	7.38	7.78	−2.08	7.19	8.14	5.10	3
S8	7.39	7.72	−2.14	7.14	8.12	5.08	4
S10	6.73	6.62	0.62	7.58	7.63	4.98	5
S2	6.36	6.76	0.83	8.34	6.67	4.94	6
S6	7.03	7.63	−2.37	7.19	8.13	4.93	7
S5	6.99	7.58	−2.42	7.19	8.10	4.89	8
S1	6.10	6.46	0.98	8.43	7.20	4.86	9
S3	6.03	6.39	1.18	8.28	7.08	4.82	10
S12	6.29	6.48	0.05	7.58	8.37	4.79	11
S11	6.05	6.22	−0.89	7.54	8.01	4.50	12
MT4	7.04	1.61	4.09	6.17	8.05	4.15	13
JS3	3.35	4.36	1.96	8.26	8.19	3.70	14
JS2	3.07	4.77	0.75	8.23	8.17	3.56	15
JS1	2.26	4.23	2.38	7.95	7.96	3.36	16
JS4	3.02	3.53	1.87	7.68	8.13	3.32	17
XJ1	3.96	2.48	1.02	8.22	7.57	3.23	18
MT3	6.50	0.62	0.92	5.49	7.46	3.22	19
XJ3	4.86	1.84	−0.56	8.12	8.59	3.19	20
MT2	5.84	1.17	−0.35	6.05	6.95	3.02	21
XJ4	4.12	2.10	−0.90	8.12	8.47	2.98	22
DYT4	5.36	1.75	−1.57	7.34	5.71	2.91	23
XJ2	4.14	1.48	−1.63	8.21	8.47	2.75	24
MT1	5.76	0.56	−3.15	7.23	6.89	2.59	25
DYT1	4.79	1.12	−2.94	6.84	6.12	2.38	26
LJ2	2.11	1.64	−0.77	8.03	7.24	2.20	27
DYT3	4.52	0.52	−2.65	6.88	6.24	2.20	28
DYT2	5.23	0.37	−4.18	6.10	7.51	2.18	29
LJ5	0.55	2.48	−1.26	8.16	6.77	1.88	30
LJ3	0.89	1.84	−1.47	8.13	7.16	1.81	31
LJ4	0.05	2.14	−1.62	8.30	6.88	1.62	32
LJ1	0.30	1.71	−2.08	7.67	6.93	1.46	33

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