酿造酱油挥发性成份分析及其在酱油鉴别中的应用研究
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摘要
酱油是一种古老的调味品,已成为老百姓日常生活中一种必需品,我国年产酱油近500万吨,居世界第一位。我国标准将酱油分为两种,一种是纯酿造酱油(FSS),另一种是含酸水解植物蛋白调味液(AHVP)的配制酱油,在利益的驱使下,目前酱油市场中以配制酱油或酸水解植物蛋白调味液冒充酿造酱油的现象较为普遍。而酱油中的挥发性风味组分在一定程度上能反映其品质的高低以及其是否为酿造酱油,因此通过对比研究酿造酱油、酸水解植物蛋白调味液、酱油香精及焦糖的挥发性风味物质,对进一步开展酱油风味分析评价工作及建立基于挥发性风味组分的酿造酱油和非酿造酱油鉴别检验方法具有重要意义。
论文以取自酱油生产企业的纯酿造酱油和酸水解植物蛋白调味液为研究分析对象,通过分析条件对比优化选择,对其挥发性风味组分进行分析,并筛选二者的特征挥发性组分,取得了一定试验成果。这些工作主要包括以下几个方面:
(1)采用静态顶空进样、直接溶剂提取和静态顶空固相微萃取等不同的样品前处理方式结合气相色谱-质谱(GC/MS)对酿造酱油中挥发性组分进行分析,通过图谱比较发现,静态顶空固相微萃取所得的分析结果优于其他三种方式。对该前处理方式进行条件优化,优化后条件为:萃取纤维头为聚炳烯酸酯(PA)、萃取温度为40℃、萃取时间为30分钟、进样时间2分钟、氯化钠加入量为1.0 g。
(2)采用优化后的分析条件,对酿造酱油、酸水解植物蛋白调味味液以及酱油产品中的添加物酱油香精和焦糖进行挥发性成分分析,并筛选出其特征挥发性组分。分析结果如下:酿造酱油中的特征组分有乙醇、异戊醇、1-辛烯-3-醇、3-甲硫基丙醇、苯乙醇等醇类物质,即酿造酱油中还原性挥发性组分较多,而且发现1-辛烯-3-醇是区别酸水解植物蛋白调味液、酱油香精及焦糖的特征差异性组分。酸水解植物蛋白调味液中的特征组分主要为一些含吡嗪官能团的杂环类化合物,但是各吡嗪类化合物种类较多,且含量差异较大,无法选择某一含吡嗪官能团化合物来作为酸水解植物蛋白调味液的特征差异组分。另外尽管存在一些酸水解植物蛋白调味液中乙酰丙酸含量较少,甚至检测不出来。但是酱油样品中乙酰丙酸的存在仍可提示该酱油样品掺加了酸水解植物蛋白调味液,所以仍选择乙酰丙酸作为酸水解植物蛋白调味液存在的特征提示物。酱油香精存在的特征提示物有乙酸苯乙酯和甲基环戊烯醇酮,其中甲基环戊烯醇酮在酱油香精中的相对含量值高且稳定,是最为理想的特征差异组分,焦糖中的特征差异组分有5-甲基-2-呋喃甲醛和5-甲基-2-乙酰基呋喃。
(3)依据前述分析结果,提出了以下几个样品属性判定指标及其检测分析方法。5个指标分别是:①相对氧化值:反映酱油样品中还原性挥发性组分的含量,间接反映酱油样品中酿造组分的的含量,检测方法简单易行,无需仪器分析;②1-辛烯-3-醇:酿造组分存在的特征提示物,检测方法为顶空固相微萃取气质联用法,内标物定量分析;③甲基环戊烯醇酮:酱油香精存在的特征提示物,检测方法为顶空固相微萃取气质联用法,内标物定量分析;④5-甲基-2-呋喃甲醛及5-甲基-2-乙酰基呋喃:焦糖存在的特征提示物,检测方法为顶空固相微萃取气质联用法,内标物定量分析;⑤乙酰丙酸:酸水解植物蛋白调味液存在的特征提示物,检测方法为直接溶剂萃取气质联用法,其限量值为100mg/L。
(4)应用上述指标对30个酱油样品进行属性判定,检测结果分析发现国内酱油生产掺假严重,许多标识为酿造酱油的产品中不含酿造组分,标识为配制酱油的产品中不仅完全不含酿造组分,甚至也不含酸水解植物蛋白调味液,国内在酱油生产过程中均添加了酱油香精和焦糖色素。
Soy sauce is one of the oldest condiments, which has become a necessity in people’s everyday life. In our country there is an annual soy sauce output of estimated 5 million tons, ranking first in the world. According to related standards in our country, soy sauce can be classified into two kinds: one is fermented soy sauce and the other concocted soy sauce containing acid hydrolyzed vegetable protein(AHVP) seasoning. Driven by the profits, at present, many soy sauce manufacturers have been selling concocted soy sauce or acid hydrolyzed vegetable protein seasoning instead of fermented soy sauce. However, the volatile flavor components in soy sauce, to some degree, can reflect its quality and help to judge whether it is fermented soy sauce. Therefore, the comparison study of volatile flavor components in fermented soy sauce, acid hydrolyzed vegetable protein seasoning, soy sauce essence and caramel, is helpful to further evaluate flavors in soy sauce and is of great significance to construct the detecting methods of fermented soy sauce and non-fermented soy sauce, based on volatile flavor components.
In this work, completely-fermented soy sauce and acid hydrolyzed vegetable protein seasoning from soy sauce manufacturers, were investigated. After the optimization of analytical conditions, their volatile flavor components were studied and some of their characteristic volatile flavor components were screened. Meanwhile some experimental achievements were realized and the main work included the following aspects:
(1) Different sample pretreatment methods, such as static headspace sample injection, direct solvent extraction and static headspace solid phase microextraction. etc., were employed and combined with GC-MS to analyze the volatile components in fermented soy sauce. From the chromatograms it could be seen that results obtained when using static headspace solid phase microextraction were better than those obtained under other three pretreatment methods. The conditions of this pretreatment method were optimized, with Polyacrylic acid esters (PA) as extraction fiber tip, extraction temperature of 40℃, extraction time of 30min, injection time of 2min and addition of 1.0g of sodium chloride.
(2) Under the optimized analytical conditions, volatile components from fermented soy sauce, acid hydrolyzed vegetable protein seasoning, soy sauce essence which was added into the soy sauce products, and caramel were analyzed. At the same time, their characteristic volatile components were screened out, with the results as follows: characteristic volatile components in fermented soy sauce included some alcohols such as ethyl alcohol, isopentanol, 1-octene-3-ol, methylmercaptopropanol and phenethyl alcohol.etc., which means that more reducing volatile components existed in fermented soy sauce; It was also found that 1-octene-3-ol was characteristic component which could distinguish acid hydrolyzed vegetable protein seasoning, soy sauce essence from caramel. While characteristic volatile components existing in acid hydrolyzed vegetable protein seasoning were mainly heterocyclic compounds containing pyrazine functional group. However, because of diversity of its pyrazine compounds and great content difference among them, none of these compounds ontaining pyrazine functional group can be regarded as the characteristic difference component in acid hydrolyzed vegetable protein seasoning. Despite the fact that there was a small amount of levulinic acid in acid hydrolyzed vegetable protein seasoning and that levulinic acid could even not be detected sometimes, the existence of levulinic acid in soy sauce samples still could give some implication that they had been added acid hydrolyzed vegetable protein seasoning. Therfore levulinic acid was finally chosen as the characteristic component to indicate the existence of acid hydrolyzed vegetable protein seasoning. Soy sauce essence indicators included phenylethyl acetate and methyl cyclopentenolone which had a higher and stable relative content and was the ideal characteristic difference component. As for caramel, characteristic difference components included 5-methyl-2-furaldehyde and 5-methyl-2-acetylfuran.
(3) According to analytical results in the previous section, several sample judging indexes and detecting methods were proposed.①Relative oxidation value, which can reflect the content of reducing volatile components in soy sauce samples and indirectly reflect the content of fermented soy sauce in these samples, is a simple and feasible detecting method without instrumental analysis.②1-octene-3-ol, the indicator of fermented components, can be detected with a combination of headspace solid phase microextraction and GC-MS, and quantitatively analyzed when adding the internal standards.③Methyl cyclopentenolone, which can indicate the existence of soy sauce essence, can also be detected and quantitatively analyzed with the methods used in 1-octene-3-ol.④5-methyl-2-furaldehyde and 5-methyl-2-acetylfuran, as the caramel indicator, are also detected quantitatively analyzed the same way.⑤Levulinic acid, acting as the characteristic indicator of acid hydrolyzed vegetable protein seasoning, can be detected using GC-MS after direct solvent extraction, with detection limit as 100 mg/L.
(4) Then the indexes mentioned above were employed to judge 30 soy sauce samples. It was found that serious adulteration existed in domestic soy sauce. Sample labelled as fermented soy sauce didn’t include fermented components, while samples labelled as concocted soy sauce not only didn’t have fermented components, but didn’t include acid hydrolyzed vegetable protein seasoning. And soy sauce essence and caramels have been added in the production process of all domestic soy sauce.
论文以取自酱油生产企业的纯酿造酱油和酸水解植物蛋白调味液为研究分析对象,通过分析条件对比优化选择,对其挥发性风味组分进行分析,并筛选二者的特征挥发性组分,取得了一定试验成果。这些工作主要包括以下几个方面:
(1)采用静态顶空进样、直接溶剂提取和静态顶空固相微萃取等不同的样品前处理方式结合气相色谱-质谱(GC/MS)对酿造酱油中挥发性组分进行分析,通过图谱比较发现,静态顶空固相微萃取所得的分析结果优于其他三种方式。对该前处理方式进行条件优化,优化后条件为:萃取纤维头为聚炳烯酸酯(PA)、萃取温度为40℃、萃取时间为30分钟、进样时间2分钟、氯化钠加入量为1.0 g。
(2)采用优化后的分析条件,对酿造酱油、酸水解植物蛋白调味味液以及酱油产品中的添加物酱油香精和焦糖进行挥发性成分分析,并筛选出其特征挥发性组分。分析结果如下:酿造酱油中的特征组分有乙醇、异戊醇、1-辛烯-3-醇、3-甲硫基丙醇、苯乙醇等醇类物质,即酿造酱油中还原性挥发性组分较多,而且发现1-辛烯-3-醇是区别酸水解植物蛋白调味液、酱油香精及焦糖的特征差异性组分。酸水解植物蛋白调味液中的特征组分主要为一些含吡嗪官能团的杂环类化合物,但是各吡嗪类化合物种类较多,且含量差异较大,无法选择某一含吡嗪官能团化合物来作为酸水解植物蛋白调味液的特征差异组分。另外尽管存在一些酸水解植物蛋白调味液中乙酰丙酸含量较少,甚至检测不出来。但是酱油样品中乙酰丙酸的存在仍可提示该酱油样品掺加了酸水解植物蛋白调味液,所以仍选择乙酰丙酸作为酸水解植物蛋白调味液存在的特征提示物。酱油香精存在的特征提示物有乙酸苯乙酯和甲基环戊烯醇酮,其中甲基环戊烯醇酮在酱油香精中的相对含量值高且稳定,是最为理想的特征差异组分,焦糖中的特征差异组分有5-甲基-2-呋喃甲醛和5-甲基-2-乙酰基呋喃。
(3)依据前述分析结果,提出了以下几个样品属性判定指标及其检测分析方法。5个指标分别是:①相对氧化值:反映酱油样品中还原性挥发性组分的含量,间接反映酱油样品中酿造组分的的含量,检测方法简单易行,无需仪器分析;②1-辛烯-3-醇:酿造组分存在的特征提示物,检测方法为顶空固相微萃取气质联用法,内标物定量分析;③甲基环戊烯醇酮:酱油香精存在的特征提示物,检测方法为顶空固相微萃取气质联用法,内标物定量分析;④5-甲基-2-呋喃甲醛及5-甲基-2-乙酰基呋喃:焦糖存在的特征提示物,检测方法为顶空固相微萃取气质联用法,内标物定量分析;⑤乙酰丙酸:酸水解植物蛋白调味液存在的特征提示物,检测方法为直接溶剂萃取气质联用法,其限量值为100mg/L。
(4)应用上述指标对30个酱油样品进行属性判定,检测结果分析发现国内酱油生产掺假严重,许多标识为酿造酱油的产品中不含酿造组分,标识为配制酱油的产品中不仅完全不含酿造组分,甚至也不含酸水解植物蛋白调味液,国内在酱油生产过程中均添加了酱油香精和焦糖色素。
Soy sauce is one of the oldest condiments, which has become a necessity in people’s everyday life. In our country there is an annual soy sauce output of estimated 5 million tons, ranking first in the world. According to related standards in our country, soy sauce can be classified into two kinds: one is fermented soy sauce and the other concocted soy sauce containing acid hydrolyzed vegetable protein(AHVP) seasoning. Driven by the profits, at present, many soy sauce manufacturers have been selling concocted soy sauce or acid hydrolyzed vegetable protein seasoning instead of fermented soy sauce. However, the volatile flavor components in soy sauce, to some degree, can reflect its quality and help to judge whether it is fermented soy sauce. Therefore, the comparison study of volatile flavor components in fermented soy sauce, acid hydrolyzed vegetable protein seasoning, soy sauce essence and caramel, is helpful to further evaluate flavors in soy sauce and is of great significance to construct the detecting methods of fermented soy sauce and non-fermented soy sauce, based on volatile flavor components.
In this work, completely-fermented soy sauce and acid hydrolyzed vegetable protein seasoning from soy sauce manufacturers, were investigated. After the optimization of analytical conditions, their volatile flavor components were studied and some of their characteristic volatile flavor components were screened. Meanwhile some experimental achievements were realized and the main work included the following aspects:
(1) Different sample pretreatment methods, such as static headspace sample injection, direct solvent extraction and static headspace solid phase microextraction. etc., were employed and combined with GC-MS to analyze the volatile components in fermented soy sauce. From the chromatograms it could be seen that results obtained when using static headspace solid phase microextraction were better than those obtained under other three pretreatment methods. The conditions of this pretreatment method were optimized, with Polyacrylic acid esters (PA) as extraction fiber tip, extraction temperature of 40℃, extraction time of 30min, injection time of 2min and addition of 1.0g of sodium chloride.
(2) Under the optimized analytical conditions, volatile components from fermented soy sauce, acid hydrolyzed vegetable protein seasoning, soy sauce essence which was added into the soy sauce products, and caramel were analyzed. At the same time, their characteristic volatile components were screened out, with the results as follows: characteristic volatile components in fermented soy sauce included some alcohols such as ethyl alcohol, isopentanol, 1-octene-3-ol, methylmercaptopropanol and phenethyl alcohol.etc., which means that more reducing volatile components existed in fermented soy sauce; It was also found that 1-octene-3-ol was characteristic component which could distinguish acid hydrolyzed vegetable protein seasoning, soy sauce essence from caramel. While characteristic volatile components existing in acid hydrolyzed vegetable protein seasoning were mainly heterocyclic compounds containing pyrazine functional group. However, because of diversity of its pyrazine compounds and great content difference among them, none of these compounds ontaining pyrazine functional group can be regarded as the characteristic difference component in acid hydrolyzed vegetable protein seasoning. Despite the fact that there was a small amount of levulinic acid in acid hydrolyzed vegetable protein seasoning and that levulinic acid could even not be detected sometimes, the existence of levulinic acid in soy sauce samples still could give some implication that they had been added acid hydrolyzed vegetable protein seasoning. Therfore levulinic acid was finally chosen as the characteristic component to indicate the existence of acid hydrolyzed vegetable protein seasoning. Soy sauce essence indicators included phenylethyl acetate and methyl cyclopentenolone which had a higher and stable relative content and was the ideal characteristic difference component. As for caramel, characteristic difference components included 5-methyl-2-furaldehyde and 5-methyl-2-acetylfuran.
(3) According to analytical results in the previous section, several sample judging indexes and detecting methods were proposed.①Relative oxidation value, which can reflect the content of reducing volatile components in soy sauce samples and indirectly reflect the content of fermented soy sauce in these samples, is a simple and feasible detecting method without instrumental analysis.②1-octene-3-ol, the indicator of fermented components, can be detected with a combination of headspace solid phase microextraction and GC-MS, and quantitatively analyzed when adding the internal standards.③Methyl cyclopentenolone, which can indicate the existence of soy sauce essence, can also be detected and quantitatively analyzed with the methods used in 1-octene-3-ol.④5-methyl-2-furaldehyde and 5-methyl-2-acetylfuran, as the caramel indicator, are also detected quantitatively analyzed the same way.⑤Levulinic acid, acting as the characteristic indicator of acid hydrolyzed vegetable protein seasoning, can be detected using GC-MS after direct solvent extraction, with detection limit as 100 mg/L.
(4) Then the indexes mentioned above were employed to judge 30 soy sauce samples. It was found that serious adulteration existed in domestic soy sauce. Sample labelled as fermented soy sauce didn’t include fermented components, while samples labelled as concocted soy sauce not only didn’t have fermented components, but didn’t include acid hydrolyzed vegetable protein seasoning. And soy sauce essence and caramels have been added in the production process of all domestic soy sauce.
引文
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[44]傅若农.固相微萃取(SPME)的演变和现状[J].化学试剂. 2008, 30 (1):13-22.
[45]程劲松.气相色谱法测定白酒中的香味组分研究进展[J].酿酒科技. 2006, (8): 104-107.
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[51] S. M. LEE, B. C. SEO, Y. S. KIM. Volatile compounds in fermented and acid-hydrolyzed soysauces[J]. Food Science. 2006, 71(3): 146-156.
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[53]李继民,王彦吉,邹宁,姚丽娟.毛细管气相色谱法测定酱油中4-甲基咪唑的含量[J].中国法医学杂质. 2007, 22(3): 151-153.
[54]彭向前,石海英.顶空进样-毛细管气相色谱法检测饮料用焦糖色素中的4-甲基咪唑[J].检测与分析. 2008, 11(5): 37-39.
[55]李祥,苏秀霞,吴桂霞,杜经武,郑民锁.挤压法焦糖色素生产工艺研究[J].中国酿造. 2007, 167(2):43-45.
[56] Official method 944.10 Permanganate oxidation number. AOAC 17th edition.
[57] Pearson’s composition and analysis of foods. 9th edition, 1991, page 464.
[58]中华人民共和国卫生部,中国国家标准化管理委员会. GB/T5009.39-2003.酱油卫生标准的分析方法[S].
[59]中华人民共和国商务部. SB/T 10417-2007酱油中乙酰丙酸的测定方法[S].
[60]美国农业部. A-A-20087C Commercial item description Soy sauce[S]. April 28, 2006.
[61]欧盟. Commission regulation (EC) No 1881/2006 setting maximum levels for certain contaminants in foodstuffs[S].
[62]日本酱油标准.福建标准化信息. 1996, (4):9
[63]新加坡标准. SS 288: 1998 specification for Soy sauce [S].
[64]台湾标准. CNS 423-1993酱油(soy sauce) [S].
[65]韩国标准(KS)H2118: 2001 Soy sauce [S].
[66]李国基,耿予欢,酱油、酸水解植物蛋白、焦糖色素中乙酰丙酸的测定[J].中国酿造. 2005, (9):51-52.