Evaluation of the Flavor Characteristics of Vinegar from Different Sichuan Regions Based on Chemical Analysis and Intelligent Sensory
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Abstract: The objective of this study was to compare and analyze the quality of four kinds of traditional vinegar from Sichuan Province. Through chemical analysis methods such as automatic amino acid analyzer, high-phase liquid chromatography (HPLC) and solid-phase microextraction gas-phase-mass-spectrometry (SPME-GC-MS) technologies were used to determine and analyze the types and contents of amino acids, organic acids, and volatile organic compounds (VOCs). Finally, in addition to sensory analysis, intelligent sensory such as electronic nose and electronic tongue combined with principal component analysis (PCA) and cluster analysis (CA) were used for characterization. The results showed that: The pH and total acid ranges of the Sichuan vinegar samples were from 3.08 to 3.29, and 16.40% to 18.07%, respectively. The color parameter a* and b* values were tested to be significantly different (P<0.05). A total of 17 kinds of amino acids were detected, of which alanine and glutamic acid had the highest content. Among 9 organic acids tested, including acetic acid and tartaric acid, the total organic acid content was 22.44～70.06 mg/mL, of which acetic acid and lactic acid ac-counted for more than 50% of the total organic acids, and Zigong vinegar had the highest organic acid content (70.06 mg/mL). More than 150 volatile organic compounds were detected in the experiment, of which acids (21.56%～44.34%) were the most abundant. It was found that the types and relative contents of unique flavor substances in traditional Chinese vinegar, such as esters and benzodiazepines, were found in Meishan vinegar, and it was significantly higher than Zigong and Nanchong vinegar samples. The sum of the first two principal components of PCA of electronic nose and electronic tongue was more than 98% of the cumulative variance. The difference of CA analysis between Zigong vinegar and Meishan vinegar was mainly due to the degree of astringency in sensory evaluation and the number of ketones and heterocycles in volatile organic compounds. The difference of CA of electronic tongue was mainly caused by the difference of pH, total amino acid, essential amino acid, organic acid and total acid between Zigong, Meishan and Nanchong vinegar. Chemical analysis, sensory evaluation and intelligent sensory combined with chemometric method can be used to characterize the correlation of four Sichuan vinegar samples due to differences in raw materials, processes, formulas, etc. This article can provide a practical reference for establishing a reliable characterization of Chinese vinegar, provide an effective tool for the evaluation of vinegar quality and authenticity, and help to understand the relationship between the internal and external quality characteristics of vinegar.摘要: 研究通过化学分子分析和智能感官等方法对四川不同产地晒醋品质进行比较分析。采用氨基酸自动分析仪、高效液相色谱（HPLC）、固相微萃取气相色谱与质谱联用（SPME-GC-MS）等化学分析方法对样品氨基酸、有机酸、挥发性有机物（VOCs）的种类和含量进行测定分析。通过感官评价，利用电子鼻、电子舌等智能感官结合主成分分析（PCA）和聚类分析（CA）进行表征。结果表明，四种川醋pH3.08～3.29，总酸度16.40%～18.07%，色泽中a*和b*有显著差异（P<0.05）；共检出17种氨基酸，其中，丙氨酸和谷氨酸含量最高；测定乙酸、酒石酸等9种有机酸，总含量在22.44～70.06 mg/mL，其中，乙酸和乳酸占总有机酸的50%以上，自贡醋样品的有机酸含量最高（70.06 mg/mL）；共检出150多种挥发性有机化合物，其中，酸类（21.56%～44.34%）含量最丰富，眉山醋样中酯类和苯二氮类化合物等种类和相对含量较高；电子鼻、电子舌PCA的前两个主成分之和超过累计方差的98%，电子鼻CA分析显示自贡和眉山醋样差异较大，可能与其感官评价中的涩味及挥发性有机物中酮类、杂环类等的数量有关，电子舌CA分析显示自贡与眉山和南充醋样差异较大，则可能是由pH、总氨基酸、必需氨基酸、有机酸和总酸的差异引起的。通过化学分析、感官分析、智能感官评价结合化学计量法，可以用来表征样品因原料、工艺、配方等因素引起差异的相关性。本研究为建立可靠的中国食醋风味表征提供实用参考，为食醋质量和真实性评价提供了有效依据。
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Figure 1. HPLC chromatogram of different organicacids standard solution
Note: 1. n-propionic acid; 2.oxalic acid; 3.tartaric acid; 4.pyruvic acid; 5.malic acid; 6.α-ketoglutaric acid; 7.lactic acid; 8.acetic acid; 9.citric acid; 10.fumaric acid; 11.succinic acid.
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Figure 2. Substance classification statistics of flavor counpounds（a） and relative content（b） in vinegar samples
Table 1 The details of the vinegar samples utilized in the experiment
Sample Name Raw materials Production area 1 Taiyuanjing water, bran, rice, vinegar koji, caramel Zigong 2 Langzhou water, bran, rice, vinegar koji, wheat, sugar, salt Nanchong 3 Qianhe water, glutinous rice, wheat, sorghum, corn, buckwheat, sugar, salt Meishan 4 Baoning water, bran, rice, glutinous rice , wheat, corn Nanchong 
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Table 2 Sensory evaluation rules of the vinegar
Sensory
characteristicsScoring item Method[30] score Appearance color pour into the colorimetric tube，
observe under a white backgroundfrom 0 to10
0: none;
1~2: very weak;
3~4: ordinary;
5~6: moderate;
7~8: strong;
9~10: very strongclarity pour colorimetric tube to observe
the presence of suspended solids and impuritiesAroma
（Flavor）ester pour into the bottle with a soft shaking its aroma burnt vinegar Taster sweet dropper take a little into the tongue and
coated with mouth to identify the tastesour umami Mouth-feel astringency
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Table 3 Physicochemical properties of four Chinese vinegars in Sichuan
Index Sample 1 Sample 2 Sample 3 Sample 4 Total sugar (g/100 g) 0.92±0.04a 0.45±0.01c 0.40±0.01c 0.65±0.02b Total acid (%) 18.07±0.96a 17.62±0.82a 16.40±0.76b 16.57±0.75b pH 3.29±0.06a 3.15±0.05b 3.08±0.05b 3.15±0.04b L* −15.51±0.22a −13.67±0.39b −12.08±0.87b −15.03±0.34a a* 1.55±0.15c 1.09±0.10d 6.64±0.21a 2.42±0.16b b* -1.32±0.19b 1.18±0.21c 3.33±0.40a -0.86±0.19d Note: Different lowercase letters in the same line indicate significant differences （P<0.05）. Table 4~Table 5 were the same.
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Table 4 The amino acids content of four Chinese vinegars in Sichuan (mg/100 mL)
Amino acids Taste threshold[33] Sample 1 Sample 2 Sample 3 Sample 4 MSG-like AA Asp 100 98.56±0.73a 26.19±0.38d 51.74±0.48c 60.75±0.57b Glu 30 129.12±1.04c 119.13±1.29d 142.67±0.90b 161.74±1.12a Lys* 50 103.06±1.37a 16.37±0.21d 49.38±0.77c 54.82±0.77b Total / / 330.74 161.69 243.79 277.31 Sweet AA Pro 300 183.55±1.43a 71.92±0.68c 66.09±0.76d 112.21±0.96b Thr* 260 69.51±0.70b 45.06±0.41c 36.92±0.41d 74.36±0.62a Ser 150 107.64±0.63a 63.55±1.24c 53.87±0.75d 92.42±1.12b Gly 130 103.92±1.09a 56.92±1.22c 41.96±1.00d 82.73±0.93b Ala 60 385.04±0.92a 217.35±1.24c 113.02±0.76d 254.41±1.08b His* 20 20.64±0.23a 2.80±0.04d 18.82±0.20b 8.79±0.11c Total / / 870.3 457.6 330.68 624.92 Bitter AA Val* 40 173.60±1.29a 98.38±1.33c 72.16±1.08d 134.32±0.91b Met* 30 32.83±0.33b 31.96±0.54c 23.52±0.27d 41.68±0.40a Ile* 90 98.54±0.90b 72.67±0.44c 44.98±0.65d 105.48±0.88a Leu* 190 225.39±1.92a 159.74±1.67c 106.41±1.13d 218.58±1.63b Phe* 90 81.96±0.84a 48.00±0.62c 60.24±0.60b 80.94±0.84a Total / / 612.32 410.75 307.31 581 Tasteless AA Cys / 6.87±0.26b 8.99±0.39a 3.34±0.23c 7.50±0.34b Tyr / 33.37±0.53a 19.48±0.32b 18.69±0.39c 32.80±0.67a Arg / 89.20±0.96a 39.84±0.51c 24.91±0.39d 54.55±0.71b Pro / 183.55±1.43a 71.92±0.68c 66.09±0.76d 112.21±0.96b Total / / 312.99 140.23 88.12 207.06 Essential AA / / 805.53 474.98 412.43 718.97 Total AA / / 2126.35 1170.27 969.9 1690.29 Note: * represents the essential amino acids.
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Table 5 The organic acids content ,flavor profile and flavor threshold of four Chinese vinegars in Sichuan (mg/mL)
Organic acids Description of flavor profile Flavor threshol Sample 1 Sample 2 Sample 3 Sample 4 Lactic acid slightly astringent, mild acid 0.19 22.06±0.40a 10.73±0.09c 5.69±0.07d 20.52±0.23b N-propionic acid / / 18.20±0.33a 1.95±0.04d 2.75±0.07c 4.88±0.15b Citric acid refreshing, fresh sour taste 0.40 12.09±0.11a 2.88±0.08c 2.73±0.03d 4.68±0.04b Acetic acid pungent sour taste 0.18 11.75±0.14a 8.86±0.05c 9.23±0.10b 6.22±0.04d Malic acid pleasant sour taste 0.49 2.41±0.09a 1.37±0.06c 1.12±0.03d 2.08±0.07b Tartaric acid slightly astringent, strong sour taste 0.47 1.52±0.07a 0.56±0.04c 0.43±0.01d 0.76±0.02b Pyruvic acid sour, salty 0.31 0.77±0.02a 0.14±0.01c 0.11±0.01d 0.22±0.01b Oxalic acid an astringent taste of acid 0.24 0.59±0.04a 0.43±0.02b 0.28±0.01d 0.36±0.01c Succinic acid contains a sour, salty, bitter taste 0.23 0.67±0.02a 0.13±0.01c 0.10±0.01d 0.41±0.01b Total (9) / / 70.06 27.05 22.44 40.13
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Table 6 The relative content of volatile flavor compounds (>1.00%) in sample vinegar
Compounds Relative content （%） Sample1 Sample2 Sample3 Sample4 Total esters (4/24) 29.47 24.79 23.34 4.64 Ethyl acetate 2.15 5.95 3.02 3-methylbutyl 2-hydroxypropanoate 3.83 Isoamyl acetate 4.73 Phenethyl acetate 0.72 0.25 2.84 0.35 Total alcohols (4/14) 8.14 0.02 4.26 16.88 2,3-Butanediol 4.36 1.15 13.99 Phenethyl alcoho 2.79 2.02 (R,R)-2,3-Butanediol 1.69 Furfuryl alcohol 1.01 0.73 Total acids (5/20) 33.08 44.34 35.62 21.56 Glacial acetic acid 26.45 38.00 35.43 19.65 Butanedioic acid, monopropargyl ester 5.38 3-chloro-2,2-dimethyl-Propanoic acid 2.59 L-(-)-3-Phenyllactic acid 0.01 1.35 3-methyl-4-oxo-Pentanoic acid 1.35 Total aldehydes (1/10) 12.87 0.6 3.77 18.08 Furfura 12.2 2.76 16.52 Total ketones (3/8) 9.05 12.78 9.03 6.22 2-methyl-3-Heptanone 7 7.12 8.98 4.18 2-Hydroxy-2-butanone 0.83 3.84 1.94 3-Hydroxy-2-butanone 0.75 1.82 0.08 Total heterocyclic (6/22) 15.72 25.07 3.68 5.45 3,5-dimethyl-1H-Pyrazole-1-methanol, 12.95 2-Pentadecyl-1,3-dioxepane 6.63 9.35 2.68 1.44 Tetramethylpyrazine 3.7 0.47 2,3,5-Trimethylpyrazine 2 0.08 2-pentadecyl-1,3-Dioxepane, 0.36 1.07 2,4,5-trimethyl-1,3-oxazole 1.01 Total benzodiazepines (3/30) 5.28 7.64 14.28 2.33 Isobutylbenzene 9.4 1,2,3,5-tetramethyl-Benzene, 2.41 2.27 1,2,3,4-tetramethyl-Benzene, 1.76 Total others (3/23) 2.13 3.15 3.61 1.56 ethyl-Hydrazine, 1.51 1.94 methoxy-phenyl-Oxime-, 1.54 0.14 0.43 1,2,3,4-tetramethyl-5-methylene-1,3-Cyclopentadiene, 0.91 1.1 Total compounds (26/151) 90.95 93.72 91.01 76.72
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