CN1681395A - 在热加工食品中降低丙烯酰胺的形成的方法 - Google Patents

在热加工食品中降低丙烯酰胺的形成的方法 Download PDF

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CN1681395A
CN1681395A CNA038224461A CN03822446A CN1681395A CN 1681395 A CN1681395 A CN 1681395A CN A038224461 A CNA038224461 A CN A038224461A CN 03822446 A CN03822446 A CN 03822446A CN 1681395 A CN1681395 A CN 1681395A
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文森特·艾伦·艾尔德
约翰·乔治亚·弗彻
亨瑞·金-航·梁
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Abstract

降低热加工食品中的丙烯酰胺量的方法和装置。本发明能够制造丙烯酰胺水平大大降低的食品。本方法依赖于阻碍丙烯酰胺形成的途径，这种丙烯酰胺形成途径以天冬酰胺氨基酸开始。

Description

在热加工食品中降低丙烯酰胺的形成的方法
                             发明背景
1. 技术领域
本发明涉及一种在热加工食品中降低丙烯酰胺量的方法。本发明在制造食品时能够使丙烯酰胺水平大大降低。本方法依赖于阻碍丙烯酰胺形成的途径，这种丙烯酰胺形成途径以天冬酰胺氨基酸开始。
2. 现有技术描述
化学丙烯酰胺已经以聚合物形式在工业应用中用于水处理、浓缩油回收、造纸、絮凝剂、增稠剂、矿石处理和免烫纤维制品。最近，丙烯酰胺单体在许多食品的检测中呈阳性。特别是在用高温加工的碳水化合物食品产品中已发现了丙烯酰胺。在丙烯酰胺的检测中呈阳性的食品的例子包括咖啡、谷类食品、曲奇、薯片、饼干、油炸马铃薯条、面包和面包卷以及沾滚上面包屑的炸肉。由于食品中的丙烯酰胺是最近发现的现象，所以其形成机理还尚未确定。但是，由于在食品产品中并不希望有丙烯酰胺单体，所以有一种在热加工的食品中显著降低或去除丙烯酰胺单体的方法是很有用的。
                             发明简述
本发明是一种在热加工食品产品中降低丙烯酰胺量的方法，本方法在一个实施例中包括：提供含有天冬酰胺的食品配料，将含有天冬酰胺的食品配料加到天冬酰胺活性减低装置中，在一种食品混合物中将含有天冬酰胺的食品配料用作一种成分，将该食品混合物加热以形成一种热加工食品。在热加工之前，通过降低在食品或食品配料中出现的活性天冬酰胺来有效地降低丙烯酰胺。在一个实施例当中，将天冬酰胺与天冬酰胺酶接触以将天冬酰胺变成天冬氨酸和氨。在另一个实施例当中，在将制造热加工食品产品中使用的食品配料以约80℃以上的温度加热之前，将食品配料沥滤以去除天冬酰胺。在本发明的再一个实施例当中，将在制造食品产品中所使用的配料发酵以降低天冬酰胺，因为微生物会使天冬酰胺通过新陈代谢发生变化而产生蛋白质合成和其它的微生物新陈代谢。
在下面的书面详细描述中，就会明显地看出本发明上面的和其它的特征和优点。
                             发明详细描述
天冬酰胺在热加工食品中的形成要求有碳源和氮源。假定碳由碳水化合物源提供，氮由蛋白质源或氨基酸源提供。许多来自植物的食品配料，如大米、小麦、玉米、大麦、大豆、马铃薯和燕麦都含有天冬酰胺，而且主要是含有较少氨基酸成分的碳水化合物。一般来讲，这样的食品配料具有小的氨基酸库，而氨基酸库除了天冬酰胺之外还含有其它的氨基酸。构成蛋白质并可在这些食品配料中找到的标准氨基酸有二十种，这些氨基酸包括但并不仅限于赖氨酸、丙胺酸、天冬酰胺、谷酰胺、精氨酸、组氨酸、甘氨酸和天冬氨酸。
通过“热加工”的意思是指将食品和食品配料，此处指食品成分，如食品配料的混合物以最低80℃加热。优选食品或食品配料的热加工在约100℃到205℃的温度下进行。在最终食品产品制成之前，可对食品配料以升高的温度进行单独的加工。热加工食品配料的一个例子是马铃薯片，这种马铃薯片用将马铃薯原料暴露在高达200℃的温度下的方法制成。其它热加工食品配料包括加工过的燕麦、煮成半熟并干燥的大米、熟大豆产品、玉米湿润粉糊、炒咖啡豆和炒可可豆。作为选择，食品配料原料可用在最终食品产品的制备中，该最终食品产品的生产包括加热步骤。其最终食品产品通过加热步骤产生的原料加工的一个例子是用生的马铃薯切片制造薯片，这种加工通过以约100℃到205℃的温度煎炸的步骤或以类似的温度生产油炸马铃薯条来进行。
不过，根据本发明，当将氨基酸天冬酰胺加热时有单糖出现时，已发现有大量的丙烯酰胺形成。在将诸如赖氨酸和丙胺酸的氨基酸加热时有如葡萄糖的单糖出现时，不会导致丙烯酰胺的形成。但令人意外的是，在有单糖出现的情况下，天冬酰胺与另一种氨基酸如赖氨酸的出现不会导致丙烯酰胺形成的增加而大大多于天冬酰胺仅是单独的一种氨基酸的情况。
在已经确定了当将天冬酰胺加热时有单糖出现时会有丙烯酰胺的快速形成的情况下，就可通过减低天冬酰胺的活性来实现在热加工食品中降低丙烯酰胺。通过“减低活性”是指通过转化方式或结合到另一种干扰丙烯酰胺从天冬酰胺形成的化学品的方式将丙烯酰胺从食品中去除或使天冬酰胺沿着丙烯酰胺的形成路径不起反应。
这样的减低活性的一个方法是将天冬酰胺与天冬酰胺酶接触。这种酶将天冬酰胺分解成天冬氨酸和氨。通过沥滤也可在热加工食品中将天冬酰胺的活性减低而形成丙烯酰胺的前体。在将一种水溶液的pH值保持在微酸或微碱优选pH值介于5至9的情况下，就会有利于天冬酰胺在这种水溶液中的溶解。通过发酵也可在热加工食品中将天冬酰胺的活性减低而形成丙烯酰胺的前体。天冬酰胺也可加入到蛋白质中以将天冬酰胺的活性减低而形成丙烯酰胺的前体。通过加入二价阳离子如乳酸钙、柠檬酸钙或苹果酸钙形式的钙也可将天冬酰胺的活性减低而形成丙烯酰胺的前体。通过加入葡萄糖、果糖或鼠李糖的方法在食品中增加还原糖的量也可将天冬酰胺的活性减低而形成丙烯酰胺的前体。
以干扰丙烯酰胺的形成的方法实现将天冬酰胺的活性减低的其它技术对于本领域的熟练技术人员来说是显而易见的。在热加工之前食品配料或食品产品中具有较低水平的天冬酰胺的情况下，最终加工的食品中的丙烯酰胺水平就会大大降低。
本发明的几个实施例在下面的例子中进行描述：
例子1：
这个例子表明在出现单糖和氨基酸赖氨酸的情况下没有形成丙烯酰胺。将约0.2克的葡萄糖在20ml的顶空进样瓶中与约0.1克的氨基酸L-赖氨酸水合物和0.2ml的水化合。该顶空进样瓶用铝箔盖上并以如下温度特征在气相色谱炉中加热：起始温度设置是40℃；然后将温度每分钟升高20℃直到200℃；在200℃停留两分钟；然后将顶空进样瓶冷却到40℃。加热之后将混合物干燥，这时混合物变黑。反应混合物用100毫升的水进行提取，且水中的丙烯酰胺通过GC-MS进行测量。在将葡萄糖与L-赖氨酸水合物加热时，没有检测到丙烯酰胺(检测极限少于10亿分之50)。如果美拉德反应是丙烯酰胺的来源，那么这种赖氨酸反应混合物应已经含有丙烯酰胺，因为该反应混合物大范围地呈褐色。
例子2：
这个例子表明在出现单糖和氨基酸丙胺酸的情况下没有形成丙烯酰胺。除了所使用的氨基酸是L-丙胺酸之外，重复例子1中的方法。同样，在超过10亿分之50的检测极限的情况下，没有能够测量到丙烯酰胺。
例子3：
这个例子表明在出现单糖和天冬酰胺的情况下丙烯酰胺的形成。除了氨基酸是L-天冬酰胺一水化物之外，重复例子1。在反应混合物用水和通过GC-MS测量的丙烯酰胺进行提取时，测量到反应混合物中有10亿分之55,106份的丙烯酰胺。按天冬酰胺的起始0.1克的量计算，生成的丙烯酰胺约有9％。
例子4：
这个例子表明在出现单糖、天冬酰胺和另一种氨基酸的情况下丙烯酰胺的形成。除了等份的L-赖氨酸水合物和L-天冬酰胺一水化物每种有0.1克之外，重复例子1。对反应混合物进行丙烯酰胺测试，发现有10亿分之214,842份的丙烯酰胺。按天冬酰胺和赖氨酸的起始量计算，生成的丙烯酰胺约有37％。
例子5：
这个例子表明在出现天冬酰胺酶的情况下，对天冬酰胺和葡萄糖进行加热时降低丙烯酰胺的形成。将这种天冬酰胺酶溶解在pH值为8.6的0.05M三盐酸缓冲液中以制备活性天冬酰胺酶溶液。对照天冬酰胺酶溶液也通过将所述活性天冬酰胺酶溶液的一部分以100℃加热20分钟以减低这种酶的活性来制成。在该对照溶液中，将0.2克的葡萄糖、0.1克的天冬酰胺和20mil的热天冬酰胺酶溶液在20ml的顶空进样瓶中化合。在活性酶试验中，将0.2克的葡萄糖、0.1克的天冬酰胺和20mil的活性天冬酰胺酶溶液在20ml的顶空进样瓶中化合。在所述顶空进样瓶中的酶的量为250个酶单位。将所述对照和活性酶混合物都制备成两份。所述顶空进样瓶都在37℃保持两个小时，然后在80℃的炉中放置40小时进行蒸发使其干燥。加热之后，在每个顶空进样瓶中加入0.2ml的水。然后将这些顶空进样瓶以如下温度特征在气相色谱炉中加热：以起始温度40℃开始；然后将温度每分钟升高20℃直到200℃；在200℃停留两分钟；然后冷却到40℃。反应混合物用50ml的水进行提取，且水中的丙烯酰胺通过GC-MS进行测量。所测得的值在下表中示出：
                            表1
       在出现天冬酰胺酶和葡萄糖的情况下丙烯酰胺的形成
实验材料           丙烯酰胺(ppb)       降低的百分率
对照               1334,810            ------
对照               2324,688            ------
活性天冬酰胺酶1    66                  99.9
活性天冬酰胺酶2    273                 99.9
正如可以看到的那样，用将天冬酰胺分解成天冬氨酸和氨的酶对所述体系进行处理将丙烯酰胺的形成降低了99.9％以上。这个实验证明降低天冬酰胺的浓度或天冬酰胺的活性会减少丙烯酰胺的形成。
除了减低天冬酰胺的活性之外，来自植物的食品配料也可以从天冬酰胺水平低于类似植物的植物中培养和选取。来自植物的食品配料中天冬酰胺的降低会在丙烯酰胺的量中反映出来，这种丙烯酰胺在相同的热处理条件下形成。
在通过参考一个实施例对本发明进行了特别说明和描述之后，本领域的熟练技术人员就会理解也可以采用其它不同的方法来减低天冬酰胺的活性，而并不背离本发明的精神和范围。

Claims (26)

1.一种降低热加工食品中的丙烯酰胺的方法，这种方法包括以下步骤：
(a)提供含有天冬酰胺(asparagine)的食品配料；
(b)在所述含有天冬酰胺的食品配料中减低天冬酰胺的活性；
(c)在食品混合物中将所述食品配料用作一种成分；和
(d)将所述食品混合物加热以形成热加工食品。
2.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述食品配料主要包括碳水化合物。
3.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述食品配料选自包括大米、小麦、玉米、大麦、大豆、马铃薯和燕麦的组。
4.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述食品配料包括马铃薯。
5.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述含有天冬酰胺的食品配料还包括至少另外一种氨基酸。
6.如权利要求5所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述至少另外一种氨基酸是赖氨酸。
7.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述减低活性步骤(b)包括在出现单糖的情况下，使所述含有天冬酰胺的食品配料与天冬酰胺酶接触。
8.如权利要求7所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述单糖包括葡萄糖。
9.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述减低活性步骤(b)包括将所述食品配料沥滤。
10.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述减低活性步骤(b)包括将所述食品配料发酵。
11.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，在所述步骤(d)将所述食品混合物加热到最低80℃的温度。
12.如权利要求1所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，在所述步骤(d)对所述食品混合物进行的热加工的温度在100℃到205℃之间。
13.用权利要求1中的方法制造的食品。
14.如权利要求13所述的食品，其特征在于，所述食品包括马铃薯。
15.如权利要求14所述的食品，其特征在于，所述食品包括薯片。
16.一种降低热加工食品中的丙烯酰胺的方法，这种方法包括以下步骤：
(a)提供含有天冬酰胺的食品配料；
(b)使含有天冬酰胺的食品配料与天冬酰胺酶接触；
(c)在食品混合物中将所述食品配料用作一种成分；和
(d)将所述食品混合物加热以形成热加工食品。
17.如权利要求16所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述食品配料主要包括碳水化合物。
18.如权利要求16所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述食品配料选自包括大米、小麦、玉米、大麦、大豆、马铃薯和燕麦的组。
19.如权利要求16所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述食品配料包括马铃薯。
20.如权利要求16所述的方法，其特征在于，所述步骤(b)中的使含有天冬酰胺的食品配料与天冬酰胺酶接触是在出现单糖的情况下进行。
21.如权利要求20所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，所述单糖包括葡萄糖。
22.如权利要求20所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，在所述步骤(d)将所述食品混合物加热到最低80℃的温度。
23.如权利要求20所述的降低热加工食品中的丙烯酰胺的形成的方法，其特征在于，在所述步骤(d)对所述食品混合物进行的热加工的温度在100℃到205℃之间。
24.用权利要求16中的方法制造的食品。
25.如权利要求24所述的食品，其特征在于，所述食品包括马铃薯。
26.如权利要求25所述的食品，其特征在于，所述食品包括薯片。
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EP1553845B1 (en) 2018-02-28
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AU2003265789A1 (en) 2004-04-08
CA2499148A1 (en) 2004-04-01
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AU2003265789A2 (en) 2004-04-08
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CN100508775C (zh) 2009-07-08
JP2006500024A (ja) 2006-01-05
RU2302745C2 (ru) 2007-07-20
EP1553845A4 (en) 2012-08-22
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RU2005112189A (ru) 2005-09-20
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