CN106133130A - 降低葡聚糖的异味产生的方法 - Google Patents
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Abstract
本发明涉及减小干燥的β葡聚糖的异味的方法。所述β葡聚糖的pH在干燥所述β葡聚糖之前降低,从而降低产生异味的美拉德反应。
Description
本申请要求保护2013年11月5日提交的美国临时专利申请序号61/900,099的优先权,其通过引用结合到本文中。
背景
本发明涉及葡聚糖生产领域。在典型喷雾干燥的酵母β葡聚糖中存在的异味水平在从品尝后略带苦味的轻微酵母味到化学味、焦味、苦味和塑料味的范围。这些味道与在美拉德(Maillard)褐变期间发展的味道一致。已知喷雾干燥条件在许多食品(脱脂干乳是重要的实例)的喷雾干燥期间影响褐变和不合需要的味道发展。控制干燥条件以使颗粒在干燥器中的加热减至最少最常用于防止热敏性产物的褐变。热敏性组分的封装也用以降低在干燥期间的产物损坏。
发明概述
β葡聚糖浆料的酸化通过抑制美拉德反应显著降低异味产生且容许在将另外在最终β葡聚糖粉末中产生令人讨厌的异味水平的条件下干燥。在干燥之前加入酸以将葡聚糖浆料的pH降低到3.0-4.0显著改进喷雾干燥的产物的味道。
本发明的以上概述并非意欲描述本发明的各个公开的实施方案或每一实施。随后的描述更特别地例示说明性实施方案。在整个申请的多个位置中,经由列出实施例提供指导,这些实施例可以不同的组合使用。在各情况下,所叙述的清单仅充当代表性集合且不应该解释为排他性清单。
附图简述
图1显示干燥的β葡聚糖的样品。
说明性实施方案的详述
美拉德反应并非单一反应,而是通常在增加的温度下在氨基酸和还原糖之间的一系列复杂反应。在该过程中,可产生数百种不同味道的化合物。这些化合物继而降解形成另外的新味道化合物。每一类型的食品具有在美拉德反应期间形成的味道化合物的非常不同的集。美拉德反应在几乎所有食品的烘烤、油炸或另外加热方面是重要的。例如,它们(部分地)负责面包、饼干、蛋糕、肉类、啤酒、巧克力、爆米花和米饭的味道。尽管已经研究了近一个世纪,但是美拉德反应如此复杂,以至于许多反应和途径尚不明确。许多不同的因素在美拉德形成中且因此在最终颜色和风味(aroma)中起作用。例如,pH(酸值)、氨基酸和糖的类型、温度、时间、氧气的存在、水、水活度(aw)及在食品基质中存在的其他食品组分在美拉德反应的结果方面都是重要的。
美拉德反应的第一步是还原糖例如葡萄糖与氨基酸的反应,其产生称为阿马道里(Amadori)化合物的反应产物。
阿马道里化合物易于异构化成三种不同的结构,这些结构可在以下步骤中不同地反应。在源自酵母的β葡聚糖中,唯一存在的糖是葡萄糖,其中反应在主链的末端且在各支链中的末端糖单元处潜在地发生。
在该反应中的接下来的步骤将根据在产物中形成的阿马道里化合物的特定异构体和在其下发生反应的条件而不同。可将氨基酸除去,且这产生最后降解成重要的味道组分糠醛和羟基甲基糠醛(HMF)的反应性化合物。其他反应为所谓的阿马道里重排,其为下列主要褐变反应的起始点。
羟基甲基糠醛(HMF)为在美拉德反应包括葡萄糖(如在用源自酵母的β葡聚糖时的情况)时美拉德反应的特征性味道化合物之一且描述为焦味、苦味和涩味的。
在阿马道里重排之后,可区分三种不同的主要途径:
•脱水反应,
•裂变,在产生短链水解产物如二乙酰和丙酮醛时,
•用氨基酸的“史崔克(Strecker)降解”或它们可缩合成醛醇。
这三种主要途径最终产生非常复杂的混合物,其包含味道化合物和褐色高分子量颜料。
已经报道葡聚糖及其他多糖(淀粉)参与美拉德反应。美拉德反应需要游离醛或酮基与氨基反应。在聚葡萄糖(glucopolysaccharide)如未分支的麦芽糊精中,这仅在各聚合物的一端存在。在支链聚葡萄糖如源自酵母的β葡聚糖的情况下,在聚合物主链的末端和在聚合物上的各个侧链的末端存在潜在的反应位点。因为在源自酵母的β葡聚糖中的1,6分支点占总键的约4-6%,这将表明在各聚合物中4-6%的总葡萄糖单元将可以参与美拉德反应。由于该少量可利用的葡萄糖单元,先前并未将其认为是异味的可能成因。
蛋白质含量和氨基酸类型将影响由美拉德褐变产生的最终产物的速率和类型两者。基于氮含量,计算可分散的源自酵母的β葡聚糖,通常含有1.5-2.5%蛋白质。该蛋白质水平比美拉德反应所研究的许多体系(NFDM、乳清粉和蔬菜粉)中的低,但仍然应当十分足以支持经由美拉德途径引起的褐变。
最新证据表明在壳聚糖中发现可分散的源自酵母的β葡聚糖中的一些或所有氮,所述壳聚糖是葡萄糖胺的聚合形式。
已经发现壳聚糖聚合物在60℃的温度的低水分条件下对美拉德褐变敏感,所述60℃的温度的低水分条件在喷雾干燥过程期间非常经常地遇到。葡萄糖胺实质上是阿马道里化合物,其是在美拉德褐变期间由葡萄糖和氨基酸的反应形成的第一类化合物。壳聚糖可充当在与源自酵母的β葡聚糖的褐变反应中的氨基的供体,或者其可沿相同的褐变途径简单地自身降解,而不与源自酵母的β葡聚糖反应。不管怎样,由此可进行味道化合物的生产。已经报道褐变反应作为在喷雾干燥期间见到的温度和水分条件期间壳多糖聚合物分解的主要来源,其与允许在含有还原碳水化合物和蛋白质的食品中的美拉德褐变的那些类似。
存在先前并不把美拉德反应视为在β葡聚糖中的异味的主要起因的多个原因。首先,美拉德反应的大多数产物包括与蛋白质反应的单糖和二糖。β葡聚糖在这两者中含量都低。第二,美拉德反应不包括作为氮源的壳聚糖,所述壳聚糖而不是蛋白质为在与β葡聚糖的褐变中所包括的氮源。在文献中没有描述在来自壳聚糖的氨基和β葡聚糖之间的美拉德反应。第三,长链碳水化合物如淀粉或β葡聚糖的褐变由于可用于反应的羧基数目有限而通常并不是一个问题。第四,褐变反应大多数在液体体系中研究,而不是在喷雾干燥期间或刚好在喷雾干燥之后出现的低水活性下研究。
在处于3.5-5%的水分的脱脂乳和乳清粉中已经报道了美拉德褐变。速率依赖于温度,其中2-4的Q10表示,随着储存温度上升10℃,反应速率增加2-4倍的因子。由于在温度和美拉德褐变反应的速率之间的公认关系,控制干燥条件以使在干燥器中颗粒的整体加热最少化是已经用以降低热敏性产物的褐变的主要方法。
喷雾干燥器采用液体溶液或悬浮液且快速蒸发水,留下干燥的固体颗粒。将液体输入流雾化成热空气流且将水蒸发。固体颗粒随着水分迅速离开液滴而形成。喷嘴或旋转盘通常用于制备尽可能小的液滴,使热传递和水汽化速率最大化。液滴尺寸可为20-180μm范围,这取决于喷嘴尺寸或旋转盘的旋转速度。
干燥器设计以及干燥条件的优化集中于使产率最大化,同时限制由于加热到从产品质量观点看可接受的水平的异味和颜色产生。在确立喷雾干燥条件中通常控制的关键变量包括:干燥器原料(在喷嘴处的固含量、温度、压力)、喷雾干燥器设计(干燥室的尺寸和几何形状、喷嘴数和尺寸)和干燥器条件(入口和出口空气的温度、在干燥器中的空气流量)。
控制正喷雾干燥的产物以降低褐变主要局限于使美拉德反应物彼此隔离。所提议的方法包括:1) 引入非反应性材料以降低还原糖和氨基相互作用的机会和2) 封装热敏性组分以降低在干燥期间反应物之间的接触。
已知美拉德反应依赖于pH。碱性pH将增强引起更多颜色和味道产生的反应,而酸性条件抑制这些反应。已经广泛研究了碱性pH用于增强美拉德反应最终产物的产生的用途且被香料工业使用以产生“反应”香料。这些香料用于增强在许多类型的食品中的煮熟味。虽然已知美拉德反应在酸性条件下较慢,但这在商业上尚未用于控制在喷雾干燥期间的褐变。如上所提,降低在喷雾干燥期间的美拉德褐变的努力集中于降低在作为主要方法的喷雾干燥期间发生的加热的量,或通过分离反应物降低到较低程度。
实施例1
为了确定β葡聚糖浆料pH和喷雾干燥器温度对喷雾干燥的酵母β葡聚糖的最终(干燥的)颜色和味道的影响,执行一系列实验。将通过碱性和酸处理从酵母细胞壁中提取的酵母β葡聚糖浆料(约5重量%固含量)用作实验的起始材料。浆料的pH使用50%w/w氢氧化钠和18M硫酸调节。可使用其他酸和碱来调节浆料的pH。
初始筛选试验检验从3.0的低pH到10.3的高pH的宽范围pH与入口空气的175℃-190℃和出口空气的75℃-90℃的温度范围的组合的影响。175℃/75℃(入口/出口)的较低温度极限归因于开始粘在喷雾干燥器侧壁上的产物。
为了分析味道,将200mg样品加到200ml水中(1mg/ml的浓度)并搅拌直至粉末分散。样品由熟悉产品味道概况的多个个体品尝并对于涩味、苦味或焦味的存在评价,这味道指示美拉德反应味道。下表1显示初始筛选试验的条件和对于味道的感官分析的结果。
表1
这些初始试验表明pH对美拉德反应味道的存在或不存在具有更大的影响,其中pH 3.0样品具有较低水平的美拉德反应味道且pH 10.3样品具有较高水平的美拉德反应味道。喷雾干燥器温度对样品的整体味道具有小得多的影响。
同样收集样品并对于颜色进行分析。如在图1中所示,在所有9个样品之间的颜色变化最低。
实施例2
基于实施例1的结果,执行第二组试验以优化pH范围,以使美拉德反应味道减至最小。再次,起始材料在碱和酸处理之后为5%固含量的酵母β葡聚糖的浆料。该系列试验的目标pH范围为约3.0-5.0。样品的pH使用50% w/w氢氧化钠和18M硫酸调节。因为干燥器温度对味道具有最低的影响,所以将干燥器保持在190℃的恒定温度下,因为这还将产生最快的操作速率。下表2显示这第二组试验的条件和感官分析的结果。
表2
美拉德反应和伴随的味道通过调节进料到雾化喷雾干燥器的液体浆料的pH影响。具体地讲,对于β葡聚糖浆料,美拉德反应在约2.5-4.0的pH范围下具有最小反应速率。使用除上述酸之外的其他酸可略微改变pH范围,但仍然将在酸性范围(pH < 5)内。低pH样品集的强迫排名(pH 2.83-4.50)表明在所有样品之间仅存在少许差别且与当前可利用的商业产品相比较所有样品具有相对较低的味道。
本发明提供多种优势。如上论述,降低β葡聚糖浆料的pH降低在干燥期间的异味形成。由于异味降低,酵母β葡聚糖可配制成味道敏感性食品和饮料制剂,而无需使用更昂贵的选择,例如溶解的酵母β葡聚糖或味道掩蔽剂。在本发明的情况下,使用者还能够在将葡聚糖较长时间暴露于较高温度的条件下干燥酵母β葡聚糖,而较低程度地产生异味和颜色。这将容许葡聚糖使用降低生产成本的设备或条件干燥。实施例将包括:a) 使用价格较低廉干燥器设计,例如箱式喷雾干燥器或b) 提供较高产率但将葡聚糖暴露于较高温度的干燥条件(即,高进料速率与较高热干燥条件相组合)。另一益处在于具有降低的异味的β葡聚糖的生产可在对生产成本具有最低影响的情况下进行,因为唯一的另外步骤是加入酸以降低β葡聚糖浆料的pH。酸的成本和将其加到浆料中的时间都将是最低的。并且最后,干燥酵母β葡聚糖和含有酵母β葡聚糖的产物的稳定性由于美拉德副产物的量降低而增强。
在喷雾干燥酵母β葡聚糖期间形成的初始美拉德反应产物可具有增加在含有β葡聚糖的最终产物的热处理和储存期间其他异味发展的速率的自动催化性质。
参考文献
1. Cremer, D. R.和K. Eichner (2000). "The influence of the pH value onthe formation of Strecker aldehydes in low moisture model systems and inplant powders." European Food Research & Technology 211(4): 247-251.
2. Bensabat, L., Frampton, V., Allen, L. Hill R. 1958 "Effect ofprocessing on the ε-amino groups of lysine in peanut proteins." J. Agr. FoodChem., 6:778.
3. Fors, S. (1983). "Sensory properties of volatile Maillard reactionproducts and related compounds Non-enzymatic browning reactions, heat-treatedfoods, chemical structures." ACS Symposium series American Chemical Society215: 185-286.
4. Kroh, L. W., W. Jalyschko等人(1996). "Non-volatile reaction productsby heat-induced degradation of alpha-glucans. Part I. Analysis of oligomericmaltodextrins and anhydrosugars." Starch 48(11-12): 426-433.
5. Kroh, L. W.和A. Schulz (2001). "News on the Maillard reaction ofoligomeric carbohydrates: A survey." Nahrung 45(3): 160-163.
6. Pereyra-Gonzales, A. S., G. B. Naranjo等人(2010). "Maillard reactionkinetics in milk powder: effect of water activity at mild temperatures."International Dairy Journal 20(1): 40-45.
7. Sithole, R., M. R. McDaniel等人(1636). "Rate of Maillard browning insweet whey powder." Journal of Dairy Science 88(5): 1636-1645.
8. Zeng, L., C. Qin等人."Browning of chitooligomers and their optimumpreservation." Carbohydrate polymers 67(4): 551-558.
本文引用的所有专利、专利申请和出版物和电子可得的材料的全部公开内容都通过引用以其整体结合到本文中。如果在本申请的公开内容和通过引用结合到本文中的任何文献的公开内容之间存在任何不一致性,则以本申请的公开内容为准。以上详述和实施例仅是为了清楚地理解而给出。应理解没有由此而来的不必要的限制。本发明不限于所显示并描述的确切细节,本领域的技术人员显而易见的变化将包括在由权利要求限定的发明内。
除非另外指出,否则在说明书和权利要求中使用的表达组分的量、分子量等的所有数值都应该理解为在所有情况下由术语“约”修饰。因此,除非另外指出相反情况,否则在说明书和权利要求中陈述的数值参数都是近似值,其可根据设法通过本发明获得的所要性质而改变。最起码的是,而且并不试图限制权利要求的范围的等同原则的应用,应当依据所报道的有效数字的位数且通过应用普通四舍五入技术至少解释各数值参数。
尽管陈述本发明的广泛范围的数值范围和参数是近似值,但应尽可能准确地报道在具体实施例中陈述的数值。然而,所有数值内在地包含必然得自其相应试验测量中见到的标准偏差的范围。
Claims (12)
1.减小在干燥的β葡聚糖中的异味的方法,其包括:
使β葡聚糖浆料酸化;和
喷雾干燥所述β葡聚糖浆料。
2.权利要求1的方法,其中所述β葡聚糖浆料在喷雾干燥之前具有小于约5的pH。
3.权利要求1的方法,其中所述β葡聚糖浆料用硫酸酸化。
4.减小在干燥的β葡聚糖的生产期间的美拉德反应的方法,其包括:
将酸加到β葡聚糖浆料中;
在加热下干燥所述β葡聚糖。
5.权利要求4的方法,其中加入酸,直至所述β葡聚糖浆料具有小于约5的pH。
6.权利要求5的方法,其中干燥还包括加热到约175℃-约190℃的温度。
7.权利要求5的方法,其中所述酸为硫酸。
8.权利要求1或4的方法,其中所述β葡聚糖浆料来源于酵母。
9.干燥的β葡聚糖,其通过包括以下步骤的方法制备:
使β葡聚糖浆料酸化;和
喷雾干燥所述β葡聚糖浆料。
10.权利要求10的干燥的β葡聚糖,其中所述干燥的β葡聚糖来源于酵母。
11.权利要求10的干燥的β葡聚糖,其中将所述β葡聚糖酸化到2.83-4.50的pH。
12.权利要求10的干燥的β葡聚糖,其中所述β葡聚糖浆料在约175℃-约190℃的温度下喷雾干燥。
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