CN113662127A - 一种利用精油降低烤黄花鱼中杂环胺含量的方法 - Google Patents
一种利用精油降低烤黄花鱼中杂环胺含量的方法 Download PDFInfo
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Abstract
本发明公开了一种利用精油降低烤黄花鱼中杂环胺含量的方法,属于食品加工技术领域。本发明所述的方法包括如下步骤:(1)将精油与食用油混合均匀,制成精油混合油,备用;其中,精油为牛至精油、丁香精油中的一种;(2)将鱼糜和步骤(1)所述的精油混合油混合均匀,放入模具加工成鱼制品;(3)将步骤(2)的鱼制品进行熟化,得到成品鱼制品。本发明采用的精油均为天然提取物,对人体无任何毒副作用,完全符合天然、绿色、健康的发展趋势。本发明解决了现有技术中烤黄花鱼中杂环胺含量高等技术问题,具有原料廉价易得、工艺条件易于控制、对于杂环胺的抑制效果显著等优点,使烤鱼制品食用更安全,可应用于大规模生产。
Description
技术领域
本发明涉及一种利用精油降低烤黄花鱼中杂环胺含量的方法,属于食品加工技术领域。
背景技术
杂环胺是由碳、氢、氮原子组成的具有杂环芳香族结构的化合物,是鱼、肉等高蛋白食品高温热加工过程中由游离氨基酸、肌酸和还原糖的美拉德反应产物(Amadori化合物、Strecker降解醛、吡啶与吡嗪)进一步反应形成的一类致癌致突变化合物。目前科学家已从高温烹调食品中分离出了30余种杂环胺,主要包括氨基咪唑氮杂芳烃和氨基咔啉两大类。如今社会随着人们对健康要求日益增高,食物中杂环胺的形成及控制已成为目前的研究热点。
黄花鱼主要分布在中国的东海、黄海、渤海等海域,是我国重要的经济鱼,其肉质细嫩、营养丰富,是中国老百姓饭桌上常见的美食。煎、炸、烤是黄花鱼常用的加工烹调方式,且市面上的黄花鱼成品如黄花鱼罐头、黄花鱼干等,都是鱼肉经过热加工制成的成品。由于黄花鱼富含氨基酸和蛋白质,因此热加工过程中容易产生杂环胺类物质。鉴于这一安全隐患,开发天然、安全、健康且有效降低烤制黄花鱼过程中杂环胺含量是我们亟待解决的关键技术问题。
目前Liliana Rounds等人(Concentration-dependent inhibition ofEscherichia coli O157:H7and heterocyclic amines in heated ground beef pattiesby apple and olive extracts,onion powder and clove bud oil)公开将精油用于牛肉饼的制备来降低杂环胺的含量,但是鱼肉属于白肉,牛肉属于红肉,它们之间的氨基酸含量与种类不同,产生的杂环胺数量与种类不同,精油对它们中杂环胺的抑制效果也不同;也有一些文献(Assessment of the influence of some spice extracts on the formationof heterocyclic amines in meat)公开了采用一些牛至提取物来抑制牛肉中杂环胺的生成,但是由于提取物中所含的有效成分纯度不高,抑制效果并不理想。
迄今为止,没有黄花鱼烤制过程中杂环胺形成及控制的研究,也尚未见到利用精油来降低鱼、肉制品中杂环胺含量的报道。因此如何减少黄花鱼热加工过程中杂环胺含量已成为食品安全领域的关注热点之一。
发明内容
[技术问题]
黄花鱼的烤制过程中会形成杂环胺;而杂环胺的存在是食品安全的一大隐患。而目前并未有黄花鱼烤制过程中杂环胺形成及控制的研究。
[技术方案]
为了解决上述问题,本发明提供了一种基于牛至精油或丁香精油降低烤黄花鱼中杂环胺含量的方法,为水产品的质量安全特别是烤鱼肉制品的杂环胺含量控制提供新的途径。
本发明的第一个目的是提供一种利用精油降低烤黄花鱼中杂环胺含量的方法,包括如下步骤:
(1)将精油与食用油混合均匀,制成精油混合油,备用;其中,精油为牛至精油、丁香精油中的一种;
(2)将鱼糜和步骤(1)所述的精油混合油混合均匀,放入模具加工成鱼制品;
(3)将步骤(2)的鱼制品进行熟化,得到成品鱼制品。
在本发明的一种实施方式中,所述的杂环胺包括IQ(2-氨基-3-甲基咪唑并[4,5-f]喹啉)、IQx(2-氨基-3-甲基咪唑[4,5-f]喹喔啉)、MeIQ(2-氨基-3,4-二甲基咪唑并[4,5-f]喹啉)、8-MeIQx(2-氨基-3,8-二甲基咪唑[4,5-f]喹喔啉)、4,8-DiMeIQx(2-氨基-3,4,8-三甲基-3H-咪唑[4,5-f]喹喔啉)、7,8-DiMeIQx(2-氨基-3,7,8-三甲基咪唑并[4,5-f]喹啉)、PhIP(2-氨基-1-甲基-6-苯基咪唑并[4,5-b]吡啶)、Trp-P-1(3-氨基-1,4-二甲基-5H吡啶并[4,3-b]吲哚)、Trp-P-2(3-氨基-1-甲基-5H-吡啶并[4,3-b]吲哚)、AaC(2-氨基-9H-吡啶并[2,3-6]吲哚)、MeAaC(2-氨基-3-甲基-9H-吡啶并[2,3-6]吲哚)、Norharman(9H-吡啶并[3,4-b]吲哚)和Harman(1-甲基-9H-吡啶并[3,4-b]吲哚)。
在本发明的一种实施方式中,步骤(1)所述精油的添加量为精油混合油的4~20wt%。
在本发明的一种实施方式中,步骤(1)所述的食用油包括大豆油、葵花油、菜籽油、花生油等。
在本发明的一种实施方式中,步骤(2)中所述的鱼糜包括黄花鱼鱼糜、鲭鱼鱼糜、马友鱼鱼糜等。
在本发明的一种实施方式中,步骤(2)中精油混合油和鱼糜的质量比为4:100;精油和鱼糜的质量比为0.16~0.8:100。
在本发明的一种实施方式中,步骤(2)中所述的鱼制品包括鱼饼,鱼饼的大小为Φ9cm×1cm。
在本发明的一种实施方式中,步骤(3)中所述的熟化包括烤制,具体是烤制温度为230~250℃,湿度为45~55%,烤制时间为每面15~25min,共30~50min,进一步优选为烤制温度为240℃,湿度为50%,烤制时间为每面20min,共40min。
本发明的第二个目的是本发明所述的方法制备得到的成品鱼制品。
本发明的第三个目的是本发明所述的方法在食品加工领域的应用。
[有益效果]
(1)本发明采用的牛至精油是从唇形科牛至属植物牛至中提取的挥发油,为黄红色或棕红色精油,具有百里香的辛辣芳香气味,主要成份有类香芹酚;欧百里香酚;对霰花烃;a-丁香烯等30多种多酚化合物及有机化合物,牛至精油是安全、高效、绿色的纯天然活性成份比较高的添加剂;丁香精油是由桃金娘科蒲桃属乔木丁香提炼而来的挥发性芳香物质,其中成分以丁香酚、乙酰基丁香酚、石竹酚类物质为主。两种精油中的酚类物质均为天然安全的植物来源,具有良好的自由基清除能力。
(2)本发明中所添加的精油为天然植物提取物,对人体健康无任何毒副作用,完全符合天然、绿色、健康的发展趋势,且原料廉价易得。
(3)在本发明方法中烤制黄花鱼的加工以及烤制的工艺条件易于达到,产品的制作及生产成本低。
(4)采用本发明的方法可有效降低烤黄花鱼中的杂环胺的含量,对于黄花鱼中杂环胺的抑制率不低于97.74%,对于烤黄花鱼中的杂环胺抑制效果显著,适于规模化生产。而且采用本发明的方法得到的成品鱼制品中脂肪化程度在0.8~1.25mg MDA/kg之间,羰基含量在0.1~0.27nmol/mg protein之间。
附图说明
图1为实施例1所测得的黄花鱼饼的杂环胺测试谱图;其中a为实施例1样品的液相谱图,b、c、d分别为对实施例1样品中Norharman、Harman、PhIP的定量分析。
图2为实施例2所测得的黄花鱼饼的杂环胺测试谱图;其中a为实施例2样品的液相谱图,b为对实施例2样品中Norharman的定量分析。
图3为实施例3所测得的黄花鱼饼的杂环胺测试谱图;其中a为实施例3样品的液相谱图,b、c、d分别为对实施例3样品中Norharman、Harman、PhIP的定量分析。
图4为实施例4所测得的黄花鱼饼的杂环胺测试谱图;其中a为实施例4样品的液相谱图,b、c分别为对实施例4样品中PhIP、Norharman的定量分析。
图5为对比例1所测得的黄花鱼饼的杂环胺测试谱图;其中a为对比例1样品的液相谱图,b、c、d分别为对比例1样品中IQ、8-MeIQx、Norharman的定量分析。
图6为对比例1所测得的黄花鱼饼的杂环胺测试谱图;其中a、b、c分别为对比例1样品中4,8-DiMeIQx、Harman、PhIP的定量分析。
图7为对比例1与实施例1~4的挥发性有机化合物的GC-IMS三维光谱俯视图对比。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解实施例是为了更好地解释本发明,不用于限制本发明。
测试方法:
杂环胺含量的测试:
将成品鱼饼(取15份,编号1~15,每份2g)打碎,加入1mL去离子水,震荡混匀10min;加入9mL乙腈溶液(含有1%乙酸),再振荡10min;加入萃取包(4g无水硫酸镁和1g无水醋酸钠),用手剧烈振荡1min;然后6000r/min离心10min,取上清液6mL加入离心管中,其中含有900mg无水硫酸镁、300mgPSA和300mg C18EC,振荡1min;6000r/min离心5min,取1mL上清液用氮吹仪吹干,加入1mL甲醇溶液,涡旋复溶,过0.22μm滤膜后采用Aglient1290-6460液相色谱质谱仪测定鱼饼中杂环胺含量;其中,高效液相色谱-质谱联用法的色谱条件为色谱柱:Agilent C18柱(2.1mm*100mm,1.8μm);室温进样5uL;流动相A:5mmol/L乙酸铵水溶液(含0.1%甲酸),流动相B:乙腈;柱温30℃,流速为0.3mL/min,进行梯度洗脱;采集模式:ESI+。
脂肪氧化的测定方法:
采用TBA法测定了烤鱼饼的脂质氧化;其中采用的硫代巴比妥酸溶液由浓度为0.375%的2-硫代巴比妥酸、浓度为15%的三氯乙酸和浓度为0.25mol/L的盐酸溶液组成。具体方法是:向5mL硫代巴比妥酸溶液中加入1g打碎的鱼饼,之后在沸水浴中加热20分钟,用流动水冷却后,在4℃下以8000r/min离心15min,在532nm处测量上清液的吸光度;脂肪氧化程度TBARS值的计算公式如下式(1):
TBARS(mg/kg)=A532×2.77 (1)
其中,A532是上清液在532nm处的吸光度。
蛋白氧化的测定方法:
采用蛋白质羰基含量检测试剂盒(北京Solarbio科技有限公司),通过计算羰基含量,对烤黄鱼蛋白质氧化进行了测定。具体是:在0.1g烤黄鱼样品中加入1mL试剂盒中的提取液(酸性缓冲液),充分均质后,在4℃下以5000r/min离心10min;取上清液至试剂盒中的0.1mL试剂1,在室温下静置10分钟后,以12000r/min的速度在4℃下离心10分钟;上清液用作样品,按照试剂盒说明书中的步骤进行测定。
风味变化测定方法:
采用GC-IMS法测定了烤鱼饼的加入精油前后的风味对比。具体是:称1g样品加入20mL顶空瓶中,在注射前在80℃下培养15分钟;然后用进样针在85℃下注入500μL孵育样品,气相色谱柱为FS-SE-54-CB-1 15m ID:0.53mm,柱温设置为60℃;气相色谱条件设置如下:2mL/min,2min,10ml/min,8min,100ml/min,10min,150ml/min,最后10min。漂移气体流量设置为150ml/min;最终用对鱼饼风味进行分析。
实施例1
一种利用牛至精油降低烤黄花鱼中杂环胺含量的方法,包括如下步骤:
(1)将野生大黄花鱼绞碎加工为黄花鱼糜,冷藏备用;
(2)将0.4g牛至精油与9.6g大豆油混合均匀,制成精油混合油,备用;其中精油的添加量为精油混合油的4wt%;
(3)将50g步骤(1)的黄花鱼糜和2g步骤(2)的精油混合油混合均匀,放入Φ9cm模具中整形,加工成Φ9cm×1cm黄花鱼饼;
(4)将步骤(3)得到的黄花鱼饼置于烤箱中,在240℃、50%湿度条件下每面烤制20min,共40min,得到成品鱼饼。
实施例2
调整实施例1步骤(2)中精油的添加量为精油混合油的20wt%;其他和实施例1保持一致,得到成品鱼饼。
实施例3
调整实施例1中的牛至精油为丁香精油,其他和实施例1保持一致,得到成品鱼饼。
实施例4
调整实施例1步骤(2)中精油的添加量为精油混合油的20wt%且调整牛至精油为丁香精油;其他和实施例1保持一致,得到成品鱼饼。
对比例1省略牛至精油的添加
一种制备成品鱼饼的制备方法,包括如下步骤:
(1)将野生大黄花鱼绞碎加工为黄花鱼糜,冷藏备用;
(2)将50g步骤(1)的黄花鱼糜和2g大豆油混合均匀,放入Φ9cm模具中整形,加工成Φ9cm×1cm黄花鱼饼;
(3)将步骤(2)得到的黄花鱼饼置于烤箱中,在240℃、50%湿度条件下每面烤制20min,共40min,得到成品鱼饼。
将实施例1~4和对比例1得到的鱼饼进行性能测试,测试结果见表1、表2:
表1为杂化胺含量的测试结果。从表1可以看出:经过精油处理过后的黄花鱼饼经过烤制,产生的杂化胺含量有大幅下降,其中实施例2效果最明显。
表1实施例1~4和对比例1的测试结果
杂环胺 | 对比例1 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
IQ | 0.6073±0.0065<sup>b</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
IQX | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
MeIQ | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
Trp-p-1 | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
8-MeIQX | 0.7590±0.0121<sup>b</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
Norharman | 876.3333±11.8462<sup>c</sup> | 19.8643±0.0739<sup>b</sup> | 0.2927±0.0038<sup>a</sup> | 1.9427±0.0107<sup>a</sup> | 0.9173±0.0135<sup>a</sup> |
4,8-DiMeIQX | 0.5417±0.0202<sup>b</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
7,8-DiMeIQX | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
Harman | 13.2667±0.1528<sup>c</sup> | 0.9393±0.0055<sup>b</sup> | ND<sup>a</sup> | 0.0783±0.0021<sup>a</sup> | ND<sup>a</sup> |
PhIP | 37.4333±0.2082<sup>d</sup> | 0.1983±0.0032<sup>b</sup> | ND<sup>a</sup> | 0.0193±0.0006<sup>ab</sup> | 0.3750±0.0072<sup>c</sup> |
AaC | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
MeAaC | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
Trp-p-2 | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> | ND<sup>a</sup> |
总杂环胺 | 928.9413±6.8492<sup>c</sup> | 21.0020±0.0817<sup>b</sup> | 0.2927±0.0037<sup>a</sup> | 2.0707±0.0131<sup>a</sup> | 1.2924±0.0210<sup>a</sup> |
总抑制率 | — | 97.74% | 99.97% | 99.78% | 99.86% |
注:“ND”表示未检测到。
表2为氧化程度的测试结果。从表2可以看出:经过精油处理过后的黄花鱼饼经过烤制,脂肪氧化程度有大幅下降,其中实施例2和实施例4效果最明显,后者甚至与未烤制的黄花鱼氧化程度无显著性差异;经过精油处理过后的黄花鱼饼经过烤制,蛋白氧化程度有下降的趋势,其中实施例2、实施例3和实施例4与对比例1相比有较好抑制效果,三者无显著性差异,而对比例1较对比例反而有一定程度的升高。
表2实施例1~4和对比例1中样品的氧化程度测试结果
例 | TBARS(mg MDA/kg) | 羰基含量(nmol/mg protein) |
生肉 | 0.8287±0.0032<sup>e</sup> | 0.3430±0.0107<sup>a</sup> |
对比例1 | 2.0951±0.0076<sup>a</sup> | 0.1830±0.0127<sup>c</sup> |
实施例1 | 1.2233±0.0229<sup>b</sup> | 0.2637±0.0110<sup>b</sup> |
实施例2 | 0.8792±0.0078<sup>d</sup> | 0.1183±0.0057<sup>d</sup> |
实施例3 | 0.1245±0.0102<sup>c</sup> | 0.1075±0.0019<sup>d</sup> |
实施例4 | 0.8543±0.0058<sup>de</sup> | 0.1060±0.0041<sup>d</sup> |
注:生肉是未烤制的黄花鱼。
图7为对比例1与实施例1~4的挥发性有机化合物的GC-IMS三维光谱俯视图对比。从图7可以看出:实施例1~4的黄花鱼饼经过烤制与对比例1相比,风味变化程度有所不同,其中实施例1和实施例3与对比例1差别不大,实施例2和实施例4与对比例1差别较大,说明对风味影响过多。
对比例2
调整实施例2的精油含量为月见草精油;其他条件和实施例2保持一致,得到成品鱼饼。
将得到的成品鱼饼进行脂肪氧化测试,测试结果如下:
对比例2的鱼饼脂肪氧化程度为1.965±0.048mg MDA/kg,相较于对比例1的2.095±0.076mg MDA/kg无显著性差异。
Claims (10)
1.一种利用精油降低烤黄花鱼中杂环胺含量的方法,其特征在于,包括如下步骤:
(1)将精油与食用油混合均匀,制成精油混合油,备用;其中,精油为牛至精油、丁香精油中的一种;
(2)将鱼糜和步骤(1)所述的精油混合油混合均匀,放入模具加工成鱼制品;
(3)将步骤(2)的鱼制品进行熟化,得到成品鱼制品。
2.根据权利要求1所述的方法,其特征在于,步骤(1)所述精油的添加量为精油混合油的4~20wt%。
3.根据权利要求1或2所述的方法,其特征在于,步骤(1)所述的食用油包括大豆油、葵花油、菜籽油、花生油。
4.根据权利要求1~3任一项所述的方法,其特征在于,步骤(2)中所述的鱼糜包括黄花鱼鱼糜、鲭鱼鱼糜、马友鱼鱼糜。
5.根据权利要求1~4任一项所述的方法,其特征在于,步骤(2)中精油和鱼糜的质量比为0.16~0.8:100。
6.根据权利要求1~5任一项所述的方法,其特征在于,步骤(3)中所述的熟化包括烤制,具体是烤制温度为230~250℃,湿度为45~55%,烤制时间为每面15~25min,共30~50min。
7.根据权利要求1~6任一项所述的方法,其特征在于,所述的杂环胺包括2-氨基-3-甲基咪唑并[4,5-f]喹啉、2-氨基-3-甲基咪唑[4,5-f]喹喔啉、2-氨基-3,4-二甲基咪唑并[4,5-f]喹啉、2-氨基-3,8-二甲基咪唑[4,5-f]喹喔啉、2-氨基-3,4,8-三甲基-3H-咪唑[4,5-f]喹喔啉、2-氨基-3,7,8-三甲基咪唑并[4,5-f]喹啉、2-氨基-1-甲基-6-苯基咪唑并[4,5-b]吡啶、3-氨基-1,4-二甲基-5H吡啶并[4,3-b]吲哚、3-氨基-1-甲基-5H-吡啶并[4,3-b]吲哚、2-氨基-9H-吡啶并[2,3-6]吲哚、2-氨基-3-甲基-9H-吡啶并[2,3-6]吲哚、9H-吡啶并[3,4-b]吲哚、1-甲基-9H-吡啶并[3,4-b]吲哚。
8.根据权利要求1~7任一项所述的方法,其特征在于,步骤(2)中所述的鱼制品包括鱼饼。
9.权利要求1~8所述的方法制备得到的成品鱼制品。
10.权利要求1~8所述的方法在食品加工领域的应用。
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