CN100393238C - 红色色素 - Google Patents

红色色素 Download PDF

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CN100393238C
CN100393238C CNB03803140XA CN03803140A CN100393238C CN 100393238 C CN100393238 C CN 100393238C CN B03803140X A CNB03803140X A CN B03803140XA CN 03803140 A CN03803140 A CN 03803140A CN 100393238 C CN100393238 C CN 100393238C
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meat
zinc
pigments
tone
red pigments
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CN1625343A (zh
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沼田正宽
若松纯一
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Itoham Foods Inc
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00Dyes of natural origin prepared from natural sources, e.g. vegetable sources
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L13/00Meat products; Meat meal; Preparation or treatment thereof
    • A23L13/40Meat products; Meat meal; Preparation or treatment thereof containing additives
    • A23L13/42Additives other than enzymes or microorganisms in meat products or meat meals
    • A23L13/428Addition of flavours, spices, colours, amino acids or their salts, peptides, vitamins, yeast extract or autolysate, nucleic acid or derivatives, organic acidifying agents or their salts or acidogens, sweeteners, e.g. sugars or sugar alcohols; Addition of alcohol-containing products
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L17/00Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L17/00Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
    • A23L17/70Comminuted, e.g. emulsified, fish products; Processed products therefrom such as pastes, reformed or compressed products
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40Colouring or decolouring of foods
    • A23L5/42Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/43Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00Porphines; Azaporphines

Abstract

发现由血红蛋白和肌红蛋白的金属卟啉部位是锌原卟啉可以得到天然红色色素,如果制备用该天然红色色素着色的肉制品、鲸肉制品、鱼肉制品和鱼糜制品,即使不使用亚硝酸盐等发色剂,也可以得到对氧化稳定且呈现良好色调的食品。

Description

红色色素
技术领域
本发明涉及对氧化安全且呈现良好的色调的天然红色色素以及用该色素着色的食品和食品原料,进一步涉及将存在于原料肉中的血红色素转化为该色素的肉制品、鲸肉制品、鱼肉制品和鱼糜制品。
背景技术
作为可以应用到食品中的红色天然色素,可以举出从红球甘蓝的叶子提取的红球甘蓝色素、从栀子种子提取的栀子红色素、从胭脂虫提取的胭脂红色素、从辣椒籽提取的辣椒红色素、从甜菜根提取的甜菜红、从葡萄的果皮提取的葡萄果皮色素、从红曲霉提取的红曲霉色素等。这些均呈现出特有的色调,但存在色调因pH而异,或欠缺对氧化的稳定性等共同的缺点。
同样,作为畜肉和鲸肉的红色色素本身的血红色素对氧化也是不稳定的,例如加热容易甲硫氨酸(met)化。防止血红色素加热甲硫氨酸化的唯一手段是使一氧化氮配位在血红素的中心铁的第6配位点上,使之亚硝化。为了该目的,一般认为在肉制品和鲸肉制品中使用作为一氧化氮供给源的亚硝酸钠等发色剂。亚硝化的血红色素加热后对氧化也稳定,呈现良好的桃红色色调。
但是,亚硝酸盐是反应性非常高的物质,将还原性物质氧化而亚硝化、重氮化、脱氨基化。特别是与仲胺反应得到的亚硝胺具有强烈的致癌性,其使用被认为有问题。
本发明是鉴于上述事实而做的,目的在于提供对氧化稳定且呈现良好的色调的天然红色色素,以及用该色素着色的食品和食品原料,进一步提供即使不使用亚硝酸盐等发色剂,不仅对氧化稳定,而且呈现良好色调的肉制品、鲸肉制品、鱼肉制品和鱼糜制品。
发明的公开
本发明人等发现只要血红蛋白和肌红蛋白的金属卟啉部位是锌原卟啉IX络合物,就可以提供对氧化稳定且呈现良好色调的天然红色色素以及用该色素着色的食品和食品原料,进一步发现通过将肉制品、鲸肉制品、鱼肉制品和鱼糜制品中的血红色素转化为该色素,即使不使用亚硝酸盐等发色剂,对氧化也是稳定的且呈现良好的色调,从而基于该发现完成了本发明。
本发明的天然红色色素具有如下的性状。即,其0.1%水溶液在波长650~350nm处的吸收光谱在可见区于587和549nm 2处显示出最大吸收,在索雷谱带中于423nm处显示出最大吸收。还有,用HCl加2-丁酮或者75%丙酮从该水溶液提取的锌原卟啉IX络合物的吸收光谱在可见区域于584和543nm 2处显示出最大吸收,在索雷谱带中于417nm处显示出最大吸收。质量分析在m/e624.20的位置上显示出锌原卟啉IX络合物特有的峰。
此外,结构如图1所示,锌原卟啉在第5配位点与球蛋白结合,形成锌血红蛋白和锌肌红蛋白。目前,锌血红蛋白无论为氧合型还是脱氧型,均固定为T状态(紧张状态,tensestate),因此例如制备一部分配位转化为锌的杂合血红蛋白[Zn(II),Fe(II)],用于血红素中心金属的电子状态和蛋白质分子的结构之间的相互作用的研究。
但是,为了食品和食品原料的着色目的使用锌血红蛋白和锌肌红蛋白的想法根本没有发现,而且这些色素在食品和食品原料中保持极其稳定的色调,这是本发明首次发现的。
本发明中使用的天然红色色素的比例相对于食品、食品原料的重量,优选在0.05~0.5%的范围。色调的目标是添加0.1%,呈现猪肉的氧合型色调,添加0.3%,呈现牛肉的氧合型色调。
另一方面,本发明人等还发现在肉、鲸肉和鱼肉中存在的正常的血红色素的中心铁通过控制其后的制造条件置换为锌,置换后,可以保持对于氧化和pH改变极其稳定的色调。例如,如果将肉、鲸肉和鱼肉在37℃保持5天的话,血红色素的中心铁置换为锌。在某一条件下,将血红色素的中心铁置换为锌的机理本来存在于肉、鲸肉和鱼肉的肌肉中,这也是本发明首次发现的。
肉、鲸肉和鱼肉中的锌置换取决于pH,在37℃反应时,其最佳pH是5.5。置换所需的锌可以利用存在于肌肉中的锌,但如果另外添加葡萄糖酸锌或者醋酸锌的话,则可以促进置换反应。目前的情况是不存在一般食品用的锌添加剂,添加含有许多锌的食品原料,例如牡蛎肉提取物等是有效的。而且,肉、鲸肉和鱼肉中的锌置换可以通过添加磷酸盐而被促进。对于食品添加剂,添加磷酸、磷酸三钾、磷酸三钙、磷酸氢二铵、磷酸二氢铵、磷酸氢二钾、磷酸二氢钾、磷酸一氢钙、磷酸二氢钙、磷酸氢二钠、磷酸二氢钠、磷酸三钠等是有效的。
另一方面,本发明人等还发现了显示出比肌肉高数倍活性的锌置换机理也存在于肉、鲸肉和鱼肉的心脏和肝脏等中。特别是肝脏的反应的最佳温度高,在55℃反应的话,锌置换3小时就完成了。此时,反应最佳pH改变为6.0。
肝脏的活性级分存在于微粒体部分,超滤进行的分级,存在于分子量20万以上。将该微粒体级分在80℃加热30分钟,或者往反应体系中添加叠氮化物的话,不会引起锌置换。据推测活性体是酶,但认为也可以利用产生类似酶的微生物来代替肝脏。
附图说明
图1是表示锌原卟啉IX络合物和球蛋白中的组氨酸残基的结合部位的图,图2是表示pH对锌肌红蛋白的吸收光谱的改变的影响的图,图3是表示从肉组织匀浆中提取的血红素和试剂锌原卟啉IX的吸收光谱,图4是表示从肉组织匀浆中提取的血红素和试剂锌原卟啉IX的HPLC图。
实施发明的最佳方式
为了更详细地说明本发明,根据表1、表2和附图说明实施例。
实施例1(色素的光稳定性)
将把金属卟啉部位置换成锌原卟啉IX络合物的肌红蛋白(试验区)、氧合肌红蛋白(对照区1)和向还原型肌红蛋白吹入一氧化氮气体进行调节得到的亚硝基肌红蛋白(对照区2)分别以0.1%浓度溶解在0.02M磷酸缓冲液(pH5.5)中,于10℃,在2500Lux的荧光灯照射下,施行1周的退色试验。退色程度用在波长423nm处的吸光度的改变表示(表1)。
【表1】
表1荧光灯照射下的吸光度的改变
  保存天数   试验区   对照区1   对照区2
  第0天第1天第2天第3天第4天第5天第6天第7天   2.882.011.861.751.531.481.351.27   2.761.020.46-----   2.931.550.820.36----
如表1所示,对照区1在第3天,对照区2在第4天大体上退色了,与此相对,试验区的退色速度极其缓慢,在第7天还保持着红色的色调。
实施例2(色素的pH稳定性)
用1N盐酸或者1N氢氧化钠将实施例1中使用的各溶液的pH调节到pH3.0~10.0的范围,测定波长650~350nm处的吸收光谱。图2显示该结果。
如图2所示,试验区的色素在pH5.0~10.0的范围是稳定的,几乎没有发现光谱上的改变。在pH3.0~5.0的范围徐徐产生沉淀,但沉淀物的色调保持着红色。另一方面,图中没有示出,对照区1和2在pH5.0以下产生显著的沉淀,沉淀物的色调呈现甲硫氨酸型的茶褐色。
实施例3(色素的加热稳定性)
将实施例1中使用的试验区的溶液在70℃加热30分钟。在加热前后,75%丙酮提取液的吸收光谱没有改变,均在584、543和417nm的位置上显示出锌原卟啉IX络合物特有的峰。另外,加热沉淀物的色调也保持着鲜红色。
实施例4(猪肉肌红蛋白的血红素中心铁置换成锌)
将尽可能除去脂肪、结缔组织的猪腰肉绞碎后,用0.2M磷酸缓冲液(pH5.5)均质化,在37℃保持5天。保持后,用75%丙酮提取血红素,进行波长650~350nm处的吸收光谱分析和HPLC分析,与试剂锌原卟啉IX(Aldrich公司制)进行比较。HPLC条件如下。
柱:Asahipak ODP-50(4.6φ×150mm)
洗脱液:甲醇/0.01M磷酸二钠(pH9.0)(76∶24)
流速:0.5ml/min
检测:UV/VIS检测...415nm
荧光检测:激发415nm,荧光590nm
测定结果示于图3和图4中,从肉组织匀浆提取的血红素的吸收光谱的最大吸收峰和HPLC的洗脱峰均和试剂锌原卟啉IX的一致。
实施例5(肉组织匀浆的退色试验)
将实施例4中调制的猪腰肉的组织匀浆填充到折径20mm的聚乙烯套管(casing)中,在温浴中,在70℃加热30分钟后,切成5mm厚(试验区)。对于对照,在相同的组织匀浆中使用亚硝酸钠200ppm和抗坏血酸钠0.2%,将肉中的肌红蛋白亚硝基化,同样加热后切片(对照区)。退色试验在10℃、2500Lux的荧光灯照射下进行3天,用色差计(Suga试验机公司制,Color Tester)测定这之间的色调改变,用亨特a(Hunter a)值表示(表2)
【表2】
表2荧光灯照射下的亨特a值的改变
  保存时间   试验区   对照区
  第0小时第12小时第24小时第36小时第48小时第60小时第72小时   6.865.634.813.693.082.962.53   7.123.581.89----
如表2所示,对照区在第36小时完全退色,与此相对,试验区的退色速度极其缓慢,在第72小时还保持着红色色调。
实施例6(高浓度锌血红蛋白溶液的调整)
将尽可能除去脂肪、结缔组织的猪心脏绞碎后,用含有10%猪血红蛋白和0.01%葡萄糖酸锌的0.2M磷酸缓冲液(pH5.5)均质化,在37℃保持15小时。保持后,用实施例4所示的方法测定吸收光谱,确认添加的猪血红蛋白被锌置换。
实施例7(采用猪肝脏的猪肉肌红蛋白的锌置换)
往猪肝脏中加入2倍量的0.2M磷酸缓冲液(pH6.0),均质化后,加入与猪肝脏等量的猪腰肉和0.01%葡萄糖酸锌,进一步均质化,在55℃保持3小时。保持后,用实施例4所示的方法测定吸收光谱,确认了反应系统中的猪肌红蛋白被锌置换了。进一步在75℃将保持后的组织匀浆加热30分钟,确认加热后的组织匀浆的色调呈现良好的桃红色。
实施例8(使用猪肝脏的微粒体级分制备新型肉制品)
往猪肝脏中加入2倍量的卤汁(含有食盐5%、调味料2%、香料0.5%,pH7.0)并均质化后,以10,000×g离心分离20分钟。往猪腰肉中注入离心上清液35%后,按照常规方法制备猪腰肉火腿。在温浴中,按50℃-2小时、55℃-2小时、72℃-1小时的顺序进行加热,中心温度达到68℃时结束。在2℃冷却1晚后,用实施例4所示的方法测定吸收光谱,确认腰肉火腿中的肌红蛋白被锌置换了。进一步确认腰肉火腿的色调呈现良好的桃红色。
如上所述,根据本发明,可以提供对氧化稳定且呈现良好色调的天然红色色素以及用该色素着色的食品和食品原料,进一步可以提供即使不使用亚硝酸盐等发色剂,对氧化和pH的改变也稳定且呈现良好色调的肉制品、鲸肉制品、鱼肉制品和鱼糜制品。
工业实用性
本发明将存在于原料肉中的血红蛋白和肌红蛋白改变为天然红色色素,所以可以用在肉制品、鲸肉制品、鱼肉制品和鱼肉制品等中。

Claims (1)

1.一种制备包含红色色素的肉制品的方法,其特征在于,在将原料肉中的血红蛋白和肌红蛋白的金属卟啉部位置换成锌原卟啉IX络合物,从而得到对氧化稳定且呈现良好色调的天然红色色素时,上述原料肉的处理条件根据该肉的种类而选择下述(a)、(b)中的任意一种:
(a)原料肉为肉时,将用含葡萄糖酸锌或醋酸锌的缓冲液处理过的pH为5.5的上述原料肉在37℃保存;
(b)原料肉为肉的心脏或肝脏时,在pH为6.0的条件下将上述原料肉在55℃保存。
CNB03803140XA 2002-02-01 2003-01-30 红色色素 Expired - Fee Related CN100393238C (zh)

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JP025117/2002 2002-02-01
JP2002025117 2002-02-01
JP015807/2003 2003-01-24
JP2003015807A JP3949588B2 (ja) 2002-02-01 2003-01-24 天然赤色色素及び当該色素を含む食品並びに食品素材
PCT/JP2003/000924 WO2003063615A1 (en) 2002-02-01 2003-01-30 Natural red pigments and foods and food materials containing the pigments

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CN100393238C true CN100393238C (zh) 2008-06-11

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US8741402B2 (en) * 2004-04-02 2014-06-03 Curwood, Inc. Webs with synergists that promote or preserve the desirable color of meat
US8029893B2 (en) 2004-04-02 2011-10-04 Curwood, Inc. Myoglobin blooming agent, films, packages and methods for packaging
US8053047B2 (en) 2004-04-02 2011-11-08 Curwood, Inc. Packaging method that causes and maintains the preferred red color of fresh meat
US8470417B2 (en) 2004-04-02 2013-06-25 Curwood, Inc. Packaging inserts with myoglobin blooming agents, packages and methods for packaging
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WO2011142300A1 (ja) 2010-05-12 2011-11-17 天野エンザイム株式会社 バチルス属微生物由来の還元剤及びその用途
CN101948630B (zh) * 2010-09-10 2013-02-27 合肥工业大学 利用畜禽血液制备碳氧血红蛋白的方法
CN102538921A (zh) * 2011-12-29 2012-07-04 湛江南海西部石油合众近海建设有限公司 液压称重单元和万吨级液压电子秤
KR20160140790A (ko) 2014-03-31 2016-12-07 임파서블 푸즈 인크. 분쇄 고기 모조물
CN108185313A (zh) * 2018-01-14 2018-06-22 浙江省农业科学院 天然抗氧化复合腌制剂及其制备方法和应用
CN110074317A (zh) * 2019-05-21 2019-08-02 南京农业大学 一种改变原料肉色泽紫黑的方法

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BR0307543A (pt) 2004-12-07
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ATE303076T1 (de) 2005-09-15
WO2003063615A1 (en) 2003-08-07
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NO20043539L (no) 2004-08-25
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US20050089607A1 (en) 2005-04-28
CA2472339A1 (en) 2003-08-07
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AU2003211905B8 (en) 2007-07-05
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