CN101778572A - 包含多酚的组合物 - Google Patents
包含多酚的组合物 Download PDFInfo
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- CN101778572A CN101778572A CN200880101437A CN200880101437A CN101778572A CN 101778572 A CN101778572 A CN 101778572A CN 200880101437 A CN200880101437 A CN 200880101437A CN 200880101437 A CN200880101437 A CN 200880101437A CN 101778572 A CN101778572 A CN 101778572A
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- polyphenol
- polymer
- complex compound
- mixture
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Abstract
本发明提供了包含多酚和含胺基聚合物的组合物,其中,占组合物重量至少0.1%的多酚作为与聚合物形成的络合物的部分存在,而且其中该络合物是微粒的形式。本发明还提供了含胺基聚合物用于控制多酚的性质的用途和制造包含多酚和聚合物的络合物的组合物的方法。
Description
发明的技术领域
本发明涉及包含多酚的组合物。特别地,本发明涉及含有胺基的聚合物用于提供改良的含多酚组合物的用途。
发明背景
天然多酚可以在许多植物中发现,且据认为是导致源自植物的食品和饮料的许多特征-特别是颜色和味道特性-的原因。据报告它们还对于与食用高水果和蔬菜饮食或源自植物的饮料(如茶和果酒)相关的健康益处有贡献。它们具有合成、医药和工业上的价值(例如,作为抗氧化剂、抗菌剂、色素和/或紫外线吸收剂)。已知天然存在的多酚具有多种生物活性。还发现它们是用于治疗或预防以下多种多样疾病的潜在候选物:心脏疾病、溃疡形成、细菌感染、突变发生和神经病症。因此,存在着对于含有高水平多酚的产品的需求。
遗憾的是,由于多酚与产品组合物中的其它成分的强相互作用,提供具有高水平多酚的产品存在问题。例如,已知多酚与某些聚合物形成络合物在饮料中产生不需要的浑浊(参见,例如,K.J.Siebert和P.Y.Lynn,″Effect of Protein-Polyphenol Ratio on the size of Haze Particles″,Journal of the American Society of Brewing Chemists,2000,58(3),pp.117-123)。此外,多酚一般具有差的氧化稳定性,与金属离子发生相互作用,具有差的聚合稳定性和对于产品的感官特性具有强烈的影响。尤其是,经常发现多酚对食品组合物产生了不需要的涩味和苦味,从而降低了其适口性,而且在溶液中往往是高色度的,因而对某些产品带来不需要的色彩。
以前已经有人尝试提供改良的包含多酚的组合物。例如,N.Hayashi等人(″Reduction of Catechin Astringency by the Complexation ofGallate-Type Catechins with Pectin″,Biosci,Biotechnol.Biochem.,2005,69(7),pp.1306-2101)已经报告,通过与果胶络合减轻了没食子酸型儿茶素的涩味。
也有人提出,当向茶中加入牛奶时,酪蛋白类蛋白质对多酚的络合主要导致苦味的减轻(G.Luck等人,″Polyphenols,Astringency andProline-Rich Proteins″,Phytochemistry,1994,37(2),pp.357-371)。这种效应主要归因于酪蛋白胶粒(casein micelles)中存在的高度特异性的结构。
我们现发现,以前被视为不需要的多酚的某些相互作用可以有效地用来提供更好的产品特性。特别是我们发现多酚与某些类型的聚合物的络合(包括导致饮料中浑浊的一些)令人惊讶地使得允许在产品中高水平地掺入多酚而对于产品的感官特性具有最小影响和/或产品中的多酚具有提高的稳定性。
测试和定义
多酚
本文所用的术语“多酚”是指包含连接到一个或多个芳香基团上的多个羟基的一类化合物中的一种或多种。术语“芳香基团”包括芳香烃基和/或杂环芳香基。杂环芳香基包括含有氧、氮或硫的基团(如那些由呋喃、吡唑或噻唑衍生的基团)。芳香基可以是单环(例如苯的情况)、双环(例如萘的情况)或多环(例如蒽的情况)的。单环芳香基包括五元环(如由吡咯衍生的基团)或六元环(如由吡啶衍生的基团)。芳香基团可以包括含有共用其连接键的环的稠合的芳香基团。术语多酚还包括配糖的多酚(glycosidic polyphenol)和/或其衍生物(如酸、酯和/或醚)。多酚的游离形式和各种酯化、醚化和糖基化(glycosylated)形式的任何组合也包括在内。多酚可以是天然的、合成的或其混合物。通常,多酚具有小于10kDa的分子量,更优选小于5kDa,且最优选0.11至2kDa。
合成的多酚包括线性(开链)和环状多酚和低聚物(参见,例如,Handique JG,Baruah JB,″Polyphenolic compounds:an overview″,React.&Funct.Polym.,2002,52(3),pp.163-188)。
多酚的更多例子包括多巴胺、肾上腺素(epinephrine)(肾上腺素(adrenaline))、降肾上腺素(norepinephrine)(去甲肾上腺素(noradrenaline))、沙丁胺醇、姜黄素和/或其衍生物、益智酮(yakuchinone)A、益智酮B、迷迭香酸和/或其衍生物、非洲豆寇醇(paradol)及其衍生物、羟基酪醇、水飞蓟素、香豆素和/或其衍生物、七叶亭、莨菪亭、木脂素(包括芝麻酚、芝麻素、芝麻酚林或其混合物)、鼠尾草酚、橄榄苦苷、尿酸、泛醌醇、百里酚酞(thymolphtaleine)、酚酞、红花素、多孔菌酸、裂盒蕈色素、bovichinon-3、银桦素(grevillin)A、银桦素B、银桦素D、紫草素、紫草宁、茜素、红紫素、假红紫素、异茜草素、茜根定、门衣司亭、醌茜(chinizarin)、桑酮(morindon)、大黄素、芦荟大黄素、大黄酸(rhein)、大黄酚、胭脂酮酸、虫漆酸(flavokermesic acid)、胭脂红酸、鞣花酸、棘色素C(spinochrome C)、棘色素D、棘色素E、海胆色素A、红紫草素、金丝桃素、大黄酸(chrysophanic acid)、甜菜苷配基、异甜菜素、焦儿茶酚、连苯三酚、没食子酸和/或其酯、咖啡酰基酒石酸(caftaric acid)、绿原酸、elonolicacid、原儿茶酸、丁香酸、龙胆酸、咖啡酸、啤酒花酸类(hops acids)(包括葎草酮、蛇麻酮、合蛇麻酮或其混合物)、木兰醇、和厚朴酚(honokiol)、双酚类、二-间苯二酚硫化物、硫氯酚(bithionol)、溴氯苯(bromochlorophen)、二羟苯宗(dioxybenzone)、亚甲基双-苯并三唑基四甲基丁基酚(bisoctrizole)、双乙基己氧基苯酚甲氧基苯三嗪(bemotrizinol)或其混合物。
优选的是每分子包含多个酚基团的天然多酚。这些多酚包括单宁(如单宁酸)、苯丙素(phenylpropanoid)、类黄酮或其混合物。最优选的是类黄酮,因为已知它们具有高的生物活性。合适的类黄酮包括黄酮类(如藤黄菌素、芹菜苷配基、黄芩素、红桔素或其混合物)、黄酮醇类(如五羟黄酮、甘丙氨菌素、莰非醇、杨梅黄酮、非瑟酮、异鼠李亭、藿香黄酮醇(pachypodol)、甲基鼠李素(rhamnazin)、芦丁、羟乙基芦丁或其混合物)、黄烷酮类(如橙皮素、柚苷配基、圣草酚或其混合物)、3-羟基黄烷酮类(如二氢五羟黄酮、二氢莰非醇或其混合物)、异黄酮类(如染料木黄酮、黄豆苷原、黄豆黄素(glycitein)或其混合物)、新类黄酮类、黄烷-3-醇类(如儿茶素、茶黄素或其混合物)、花色素类(如花青素(cyanidin)、翠雀素、锦葵色素苷、天竺葵色素、甲基花青素(peonidin)、矮牵牛苷配基或其混合物)、或其混合物。最优选的是儿茶素、茶黄素或其混合物。另一种优选的多酚是白藜芦醇,已报告其具有许多有利的健康效应。
含胺基的聚合物
术语“含胺基的聚合物”是指一种或多种具有多个胺官能团的聚合物。胺官能团可能是伯、仲、叔、季胺或其混合。最优选的是包含杂环胺基的聚合物。杂环胺基包括那些由吡啶、哌啶、硝基吡啶、氨基吡啶、溴吡啶、吡嗪、哒嗪、嘧啶、胞嘧啶、胸腺嘧啶、尿嘧啶、喹啉、异喹啉、烟酸、邻磺酰苯酰亚胺、吡咯、硝基吡咯、吡咯烷、噻唑、咪唑、吲哚、组氨酸、脯氨酸、羟脯氨酸、色氨酸、组氨酸、嘌呤、组胺、苯胺、咖啡因衍生的基团或其混合。
通常,聚合物每分子具有至少3个胺官能团,更优选至少10个胺官能团,且最优选20至10000个胺官能团。另外地或替代地,聚合物每单体残基具有至少1个胺官能团。该聚合物通常具有至少1kDa、更优选至少5kDa、最优选10至1000kDa的重均分子量。
含胺基的聚合物可以是天然的、合成的或其混合物。合适的聚合物包括酪蛋白之外的蛋白质(例如胶原(collagen)、明胶(gelatine)、弹性蛋白(elastin)、谷醇溶蛋白(prolamin)、唾液蛋白质、乳清蛋白、大豆蛋白、它们的水解产物(hydrosylates)、它们的衍生物或其混合物)、多肽(如聚-L-脯氨酸、聚-L-色氨酸、聚-L-组氨酸或其混合物)、核酸(如DNA、RNA或其混合物)、合成聚合物(如聚(乙烯基吡啶)、聚(乙烯吡咯烷酮)、聚苯胺、聚吡咯或其混合物)、多糖(如脱乙酰壳多糖、透明质多糖(hyaluronan)或其混合物)或其混合物。最优选的谷醇溶蛋白是麦醇溶蛋白(gliadin)、玉米蛋白(zein)或其混合物。其它合适的聚合物包括黑色素。
络合物(complex)
本文所用的术语“络合物”是指至少两个分子的非共价缔合。聚合物和多酚的络合物通常是其中多酚被固定化从而使得它不能通过高分辨率1H-NMR检测到。通常可以通过加入溶剂二甲基亚砜(DMSO)解离络合物,在这种情况下,多酚对于高分辨1H-NMR是可见的。
络合物中的聚合物∶多酚的重量比优选是100∶1至1∶100的范围。不过,我们发现,可使用相对少量的聚合物与多酚络合,因此,该比例更优选是5∶1至1∶50,最优选2∶1至1∶10。
颗粒大小
本文所用的术语“颗粒大小”,是指微粒在任何维度上的最大长度。微粒可以是球形、非球形或其混合物。因此,如果微粒是球形的,那么颗粒大小是指微粒的直径。
饮料
本文所用的术语“饮料”指适于人消费的基本上水性的可饮用组合物。优选饮料包含占饮料重量至少85%的水,更优选包含至少90%的水,最优选包含至少95%至99.9%的水。
茶固体
本文所用的术语“茶固体”指可以从植物中国茶(Camellia sinensisvar.sinensis)和/或普洱茶(Camellia sinensis var.assamica)的叶子中提取的干物质。所述材料可以经历所谓的“发酵”步骤,在发酵步骤中,材料被在“红茶”加工的早期阶段中释放的特定内源性酶氧化。这种氧化作用甚至可以用外源性酶(如氧化酶、漆酶和过氧化物酶)的作用加以补充。或者,材料可以经部分发酵(“乌龙茶”)或基本上不发酵(“绿茶”)。
茶饮料
本文所用的术语“茶饮料”指包含至少0.01重量%的茶固体的饮料。优选茶饮料包含0.04%至3%的茶固体,更优选包含0.06%至2%的茶固体,最优选包含0.1%至1%的茶固体。
儿茶素类
本文所用的术语“儿茶素类”用作儿茶素、没食子儿茶素、儿茶素没食子酸酯、没食子儿茶素没食子酸酯、表儿茶素、表没食子儿茶素、表儿茶素没食子酸酯、表没食子儿茶素没食子酸酯及其混合物的通称。
茶黄素类
本文所用的术语“茶黄素类”用作茶黄素、异茶黄素、新茶黄素(neotheaflavin)、茶黄素-3-没食子酸酯、茶黄素-3′-没食子酸酯、茶黄素-3,3′-二没食子酸酯、表茶黄酸(epitheaflavic acid)、表茶黄酸-3′-没食子酸酯、茶黄酸、茶黄酸-3′-没食子酸酯及其混合物的通称。这些化合物的结构是众所周知的(参见,例如,在″Tea-Cultivation toconsumption″,K.C.Willson和M.N.Clifford(编),1992,Chapman & Hall,London,pp.555-601的第17章中的结构xi-xx)。
巧克力
本文所用的术语“巧克力”是指包含至少5%干重的由可可树(Theobroma cacao)获得的物质的可食用的组合物。巧克力优选包含至少10%干重,更优选30%至95%干重的由可可树获得的物质。巧克力优选至少是半固体,更优选在20℃是固体。巧克力优选是脂连续的(fat-continuous)。巧克力可以是黑巧克力,牛奶巧克力或白巧克力。
发明概述
在第一方面,本发明提供了一种组合物,包含:
多酚;和
含有胺基的聚合物,其中,该聚合物不是酪蛋白;
其中,占组合物重量至少0.1%的多酚作为与所述聚合物的络合物的部分存在,而且其中,该络合物是微粒的形式。
这样的组合物以多酚相对惰性(即,在味道、颜色和/或稳定性方面)但可以方便地转化为活性形式(例如,通过络合物摄取时的解离)的形式递送高水平的多酚。
在进一步的方面,本发明提供了含有胺基的聚合物用于减轻或消除多酚的苦味和/或涩味的用途,其中,聚合物不是酪蛋白。
在更进一步的方面,本发明提供了一种制造包含多酚和含胺基聚合物的络合物的组合物的方法,该方法包括以下步骤:
i)混合所述多酚和聚合物,从而形成络合物;
ii)回收所述络合物;然后
iii)将所述络合物与支持介质(supporting medium)组合。
这种方法允许不依赖于支持介质而控制所述络合物的特性。
发明详述
组合物
所述组合物包含通过络合物稳定的高水平多酚。特别是,占组合物重量的至少0.1%的多酚,优选占组合物重量的至少0.2%,更优选占组合物重量的至少0.3%,且最优选占组合物重量的至少0.5%作为络合物的部分存在。通常情况下,小于组合物重量50%,更优选小于10%,且最优选小于2%的多酚作为络合物的部分而存在。
该组合物还可能包括不是与聚合物的络合物的部分的多酚。但是,为了使多酚对产品性能的影响最小化,优选组合物中的大多数多酚作为络合物的部分存在。因此,优选在组合物中多酚总重量的至少50%,更优选至少60%,再更优选至少80%,且最优选多酚总重量的90%至100%作为与聚合物的络合物的部分存在。
优选组合物中多酚的总量足够使该组合物可以以一或两剂递送有效日摄入量。因此,优选以包含至少50mg、更优选至少150mg、最优选300mg至1g总多酚的单位剂量形式提供该组合物。为了便于运输和加工,优选该剂量形式具有小于500g的质量,更优选小于250g的质量,再更优选小于200g的质量,最优选20至150g的质量。
络合物在组合物中以微粒的形式存在。较小的微粒允许在对于某些产品性质具有最小影响的情况下掺入络合物。因此,优选至少90%重量的微粒具有小于5000nm的颗粒大小,更优选小于1000nm、800nm、600nm、400nm或甚至小于200nm。再更优选至少90%重量的微粒具有10至100nm的颗粒大小。
通常,微粒分散在支持介质中。优选支持介质构成组合物的大部分,并在很大程度上决定它的感官特性和物理特性。因此,优选组合物包含小于组合物重量50%的量的络合物,更优选小于10%,且最优选0.1%至5%。支持介质可以是任何合适的物质,且很大程度上取决于组合物的预期的最终用途。然而,通常情况下,支持介质是液体、分散体(单相或双相乳液(single or duplex emulsion)、泡沫或悬浮液)、凝胶、固体或其混合物。支持介质可以是水性的(包含占支持介质重量至少50%的水)或非水性的。在最优选的实施方式中,选择微粒的特性(特别是其大小和表面性质)以及支持介质的特性(特别是其粘度和极性)以使得微粒在支持介质中形成稳定的胶态分散体。该分散体优选是稳定的,从而在20℃的贮存温度下在至少7天的时期内,更优选至少1个月的时期内,最优选至少6个月的时期内,没有明显的沉淀出现。
本发明的组合物在络合物中除了所述聚合物外,还可能包含酪蛋白。然而,优选该组合物基本上不含酪蛋白。特别优选组合物包含小于组合物重量0.1%的酪蛋白,更优选小于0.05%,且最优选小于0.01%。这是因为酪蛋白可能竞争性地与多酚发生相互作用。
药物和化妆品组合物
在一种实施方式中,所述组合物是包含药学和/或化妆品可接受的载体的药物或化妆品组合物。
本发明的药物和化妆品组合物可以适用于任何施用形式,包括口服、局部施用和/或静脉内施用。组合物的形式尤其可以是片剂、丸剂、锭剂、糊剂、洗剂、凝胶、乳剂、液体(包括乳液和/或悬浮液)、喷雾剂(包括气溶胶喷雾剂)、泡沫或粉末。
制药或化妆品组合物包含可以用作组合物中的络合物的稀释剂、分散剂或载体的药学或化妆品可接受的载体。所述载体可能是含水或无水的。
如果存在水的话,水的量是组合物重量的5%至99%,更优选20%至70%,最佳为40%至70%。
除了水,相对挥发性的溶剂也可以包括在载体中。最优选的是一羟基的C1-C3链烷醇。这些包括乙醇、甲醇和异丙醇。
润肤材料也可以包括在载体中。这些可以是硅油和/或合成酯的形式。
多元醇类型的湿润剂也可以在载体中采用。典型的多元醇包括甘油、聚亚烷基二醇(polyalkylene glycols),且更优选亚烷基多元醇(alkylene polyol)及其衍生物。
增稠剂也可以用作载体的一部分,糖、增塑剂、抗氧化剂、抗菌剂、螯合剂、缓冲剂、着色剂、色素、遮光剂、表面活性剂、推进剂、调味剂和/或香料也可以用作载体的一部分。
优选的化妆品组合物是那些适用于人体皮肤的化妆品组合物,且优选除了所述络合物之外还包括皮肤增益剂(skin benefit agent)。合适的皮肤增益剂包括抗衰老剂、抗炎剂、抗皱剂、皮肤增白剂、抗痤疮剂、防晒剂(包括紫外线吸收剂)和/或皮脂减少剂。这些的例子包括α-羟酸、β-羟酸、多羟基酸、氢醌、叔丁基氢醌、维生素B和C及其衍生物、微粉化金属氧化物、类维生素A、桦木酸、香草酸、尿囊素、胎盘提取物、hydrolactin、间苯二酚衍生物,及其混合物。
食品组合物
组合物的特别优选的形式是食品的形式,因为这允许方便和令人愉快地摄取多酚。食品组合物可以是,例如,人造黄油、低脂涂抹料(spread)、糖果产品(如巧克力或压块干粮)、冰淇淋、调味品(dressing)、蛋黄酱、酱油、焙烤食品、起酥油(shortening)或干酪。特别优选的是食品组合物是饮料或巧克力组合物。
食品可以进行干燥,且含有小于组合物重量40%的水,优选小于25%的水,更优选1%至15%的水。或者,食品可以是基本上水性的,且包含占组合物重量至少40%的水,优选至少50%的水,更优选65%至99.9%的水。
食品优选包含包括碳水化合物(包括糖和/或淀粉)、蛋白质、脂肪、维生素、矿物质、植物营养素(包括萜类、酚类化合物、有机硫化物或其混合物)或其混合物的营养物质。食品可以是低热量的(例如,具有小于100kCal/100g组合物的能含量),或可以是高热量的(例如,具有大于100kCal/100g组合物的能含量,优选150至1000kCal/100g组合物)。
食品还可能包含盐、调味剂、着色剂、防腐剂、抗氧化剂、非营养性甜味剂或其混合物。
当食品组合物是饮料时,其优选是咖啡饮料、茶饮料和/或可可饮料。最优选该饮料是茶饮料。
饮料的pH值可以是例如2.5至8,优选3至6,更优选3.5至5。
当食品组合物是巧克力时,该组合物可以包含可可碱(3,7-二氢-3,7-二甲基-1H-嘌呤-2,6-二酮),其被认为导致巧克力的特征风味,并具有一定的生理效应。特别优选的是:组合物包含占组合物重量的至少0.1%、更优选至少0.5%,最优选1%至5%的可可碱。当食品组合物是可可饮料时,它也可能包含可可碱,更优选可可饮料包含0.05%至1%重量的可可碱,最优选0.1%至0.4%重量的可可碱。
白巧克力由于它的可可固体物质含量低,传统地具有非常低水平的多酚。我们已经认识到,通过使用本发明的络合物形式的多酚,可以制备具有更深色巧克力的健康利益的白巧克力,而不向白巧克力赋予不必要的苦味。
还可以设想,本发明的巧克力组合物可能用于糖果产品的填充料、组成成分和/或包衣。例如,巧克力可以用于包被冰冻甜点(如冰淇淋、果汁冰糕、水冰等),和/或巧克力可以分散于冰冻甜点中。
聚合物或组合物的用途
据发现,含有胺基的聚合物存在于含有多酚的组合物中减轻或消除了多酚的苦味和/或涩味。虽然不希望受限于理论,我们相信这可能是由于络合物干扰了多酚和嘴里的蛋白质和/或受体之间的相互作用。
含有胺基的聚合物可能另外地或替代地增加多酚的氧化稳定性,例如,通过使多酚较少地与氧化剂和/或催化物质相互作用。
含有胺基的聚合物可能另外地或替代地减轻或消除多酚的颜色。不希望受限于理论,我们认为,多酚与聚合物的缔合使得光散射增强,其掩盖了至少多酚的部分颜色。
据信,当聚合物和多酚之间有强的相互作用时,上述各种用途是最佳的。因此,优选至少部分多酚作为与聚合物的络合物存在。络合物优选是微粒形式,因为这使得络合物对于可能希望维持的某些其它的产品性能的影响最小化。在最优选的实施方式中,上文提出的用途采用作为根据本发明的第一方面的组合物(包括组合物的任何具体描述的实施方式)的部分的聚合物。
方法
可以以任何合适的方式制造本发明的络合物和组合物。例如,可以通过在支持介质中使聚合物和多酚接触而原位形成络合物。
然而,在优选的实施方式中,络合物不依赖于支持介质制造。该方法包括以下步骤:
i)混合多酚和聚合物,从而形成络合物;
ii)回收所述络合物;然后
iii)将所述络合物与支持介质组合。
优选在液体介质中,更优选在水性液体介质中进行步骤(i)中的混合。优选在连续搅拌下进行混合,尤其是如果络合物是作为微粒回收的。
回收步骤(ii)通常包括从液体介质中分离络合物,例如通过干燥、沉淀、过滤或其混合。干燥可以包括喷雾干燥、冷冻干燥或其混合。在最优选的实施方式中,在步骤(ii)中回收作为微粒的络合物,例如,以粉末或浓缩的悬浮液的形式。步骤(ii)可以另外地或替代地包括使用表面活性剂、聚合物、糖和/或保护胶体稳定该络合物。
组合步骤(iii)优选包括在支持介质中分散微粒形式的络合物。
当组合物包含上文所述的支持介质时,该方法特别适用于制造本发明的组合物(包括组合物的任何具体描述的实施方式)。
实施例
通过参考下面非限制性的实施例详细阐述本发明。
实施例1
在本实施例中,评估了一些候选络合剂(CA)的结合多酚的能力。也测试了所选择的CA的掩蔽多酚苦味的能力。
材料
从Roche,Switzerland获得表没食子儿茶素没食子酸酯(EGCG)。从Davisco,USA购得乳清蛋白制品(Whey protein isolate)(WPI)。从Sigma Chemicals(Schnelldorf,Germany)购得聚乙烯吡咯烷酮(PVP)、L-脯氨酸和聚-L-脯氨酸。获得3个分子量级的PVP:PVP 10具有10kDa的平均分子量,PVP 40具有40kDa的平均分子量,和PVP 360具有360kDa的平均分子量。从CP-Kelco(San Diego,USA)获得高甲氧基果胶(HMP)(~70%酯化)。
样品制备
通过向去离子水(电导率=18.2MΩ.cm)中加入粉末并在40℃下搅拌获得含有1.2重量%EGCG的原溶液。通过将PVP、WPI、L-脯氨酸和聚-L-脯氨酸溶于25℃的去离子水以获得1.2重量%的浓度来制备每种物质的原溶液。通过将粉末溶于80℃的去离子水1小时并冷却到25℃来制备果胶原溶液。在物质溶解后,使用0.01盐酸或0.1M氢氧化钠将除了WPI之外的所有样品的pH调整到5.0。WPI在pH 6.5下使用以避免乳清蛋白沉淀。在所有情况下,保持最大离子强度低于10mM。在设置pH值之后,通过在连续搅拌下快速加入固定重量的EGCG原溶液到相同重量的络合剂(CA)溶液中来制备混合系统。因此,最终的样品含有0.6重量%的EGCG和0.6重量%的CA。
动态光散射(DLS)
在样品制备后4小时之内,使用Zetasizer Nano ZS仪(MalvernInstruments,Malvern,UK)进行DLS测量。该仪器记录由含有大小为1至1000nm的微粒的澄清样品以固定的角度散射的光的强度波动。这些波动被转换成跨越皮秒和秒之间的时间尺度的自相关函数。该仪器的软件将强度计量的和体积计量的粒度分布与记录的自相关函数拟合。在25℃下,样品不经任何稀释进行测量。假设样品的粘度在所有情况下是水的粘度,且1.59的折射率用于分析中。平均颗粒大小为体积平均的平均颗粒大小。当在数据中出现多于一个峰值时,给出对应于各个峰的最大值的颗粒大小。
1H-NMR
在27℃下,5mm NMR管中,使用Bruker AV600核磁共振谱仪对0.6ml样品进行质子-核磁共振测量。在测量之前,向各样品加入5%(重量/重量)的D2O。通过使用Brucker脉冲程序noesygpprld预磁饱和水信号而获得谱图。~4.7ppm处的信号来自残留的水,且对于数据分析的目的可以忽略该信号。信号从核磁共振谱中消失表明结合以形成络合物。从EGCG溶液的浓度范围(0.1%-1.2%)获得1H NMR谱,以证明在这个范围内EGCG峰强度的线性反应。这种校准曲线用来评估样品中的非络合(或“游离的”)EGCG的量。
苦味和涩味的评估
由5个未经训练的个人确定3种含有0.6重量%EGCG的混合系统(果胶、WPI和PVP)的苦味,所述个人不知道提供的样品的组成。定性地评价样品的苦味和涩味。
结果
结果如表1所示。
表1
络合剂 | 在溶液中游离的EGCG量(重量%总ECCG) | 外观 | 平均颗粒大小(nm) | 味道 |
WPI | <0.002 | 透明 | 7,20 | 轻微苦和涩 |
络合剂 | 在溶液中游离的EGCG量(重量%总ECCG) | 外观 | 平均颗粒大小(nm) | 味道 |
L-脯氨酸 | 100 | 透明 | 2 | N.M.* |
聚-L-脯氨酸 | 0 | 透明 | 17,73 | N.M.* |
PVP 10 | 0 | 白色/混浊 | >>10000 | N.M.* |
PVP 40 | 0 | 白色/混浊 | 400 | 不苦,不涩 |
PVP 360 | 0 | 白色/混浊 | 5000 | N.M.* |
果胶 | 47 | 透明 | 400 | 非常苦和涩 |
*-N.M.=未测量。
从表1的数据可以看出,不是聚合物的L-脯氨酸并不络合多酚(100%的EGCG在溶液中是游离的)。果胶是一种聚合物,但不包含胺基。含有胺基的聚合物(WPI和PVP)都比果胶络合更多的多酚。对于含有胺基的聚合物观察到最大的掩蔽多酚苦味和涩味的能力。
实施例2
在本实施例中,使用含有多酚的络合物作为浓基质,其经稀释以获得具有需要的多酚浓度的最终产品。
材料
使用与实施例1相同的材料。
样品制备
如实施例1所述,制备含有0.6重量%EGCG和0.6重量%CA的浓基质。然后在促进混合的高剪切下将浓基质与去离子水以1∶1(重量)混合。通过光散射表征获得的产品以检查络合物是否保持稳定。
动态光散射(DLS)
如实施例1所述进行颗粒大小测定。
结果
结果如表2所示。
表2
络合剂 | 外观 | 平均颗粒大小(nm) |
WPI | 透明 | 7,20 |
络合剂 | 外观 | 平均颗粒大小(nm) |
PVP 40 | 白色/混浊 | 400 |
可以从表2的数据看出,平均颗粒大小在稀释时没有改变,系统保持稳定。
实施例3
在本实施例中,研究多酚-聚合物的络合物对于巧克力的苦味的效应。
材料
富含多酚的纯可可糖膏是来自Barry Callebout Nederland BV的″cocoa liquor CM Fine″。聚乙烯吡咯烷酮是来自BASF,Germany的″30″。所有使用的水是家用自来水。
样品制备
通过向水中加入PVP并在45℃搅拌10分钟制备2重量%的PVP溶液。然后在45℃的水浴中在玻璃瓶中熔化可可糖膏。通过将熔化的可可糖膏与水在45℃下以1∶1的重量比混合来制备第一样品(样品A)。然后通过将熔化的可可糖膏与PVP溶液在45℃下以1∶1的重量比混合来制备第二样品(样品B)。制备后5分钟,由两个测试人员以B-A的顺序盲测品尝样品。
结果
两个测试人员都指出,巧克力B明显比巧克力A苦味较轻。因此,PVP在巧克力配方中的存在可以减轻巧克力的可感知的苦味。
Claims (23)
1.一种组合物,包含:
多酚;和
含有胺基的聚合物,其中,所述聚合物不是酪蛋白;
其中,占组合物重量至少0.1%的多酚作为与所述聚合物的络合物的部分存在,而且其中该络合物是微粒的形式。
2.如权利要求1所述的组合物,其中,至少90%重量的所述微粒具有小于5000nm的颗粒大小。
3.如权利要求1或2所述的组合物,其中,所述微粒分散在支持介质中。
4.如上述权利要求中的任一项所述的组合物,其中,所述多酚选自黄酮、黄酮醇、黄烷酮、3-羟基黄烷酮、异黄酮、新类黄酮、黄烷-3-醇、花色素、白藜芦醇或其混合物。
5.如权利要求4所述的组合物,其中,所述多酚选自儿茶素、茶黄素或其混合物。
6.如上述权利要求中的任一项所述的组合物,其中,所述聚合物的重均分子量是至少1kDa。
7.如上述权利要求中的任一项所述的组合物,其中,所述聚合物是以下聚合物中的至少一种:
-包含含胺基的氨基酸的蛋白质、包含含胺基的氨基酸的多肽或其混合物;
-DNA、RNA或其混合物;
-聚(乙烯基吡啶)、聚(乙烯基吡咯烷酮)、聚苯胺、聚吡咯或其混合物,和
-含有胺基的多糖。
8.如权利要求7所述的组合物,其中,所述蛋白质选自麦醇溶蛋白、玉米蛋白、胶原、明胶、弹性蛋白、唾液蛋白质、乳清蛋白、大豆蛋白、它们的水解产物、它们的衍生物,或其混合物。
9.如权利要求8所述的组合物,其中,所述蛋白质是乳清蛋白。
10.如上述权利要求中的任一项所述的组合物,其是食品组合物。
11.如权利要求10所述的组合物,其中,所述组合物是饮料,优选茶饮料。
12.如权利要求10所述的组合物,其中,所述组合物是巧克力。
13.如权利要求12所述的组合物,其中,所述组合物是白巧克力。
14.如上述权利要求中的任一项所述的组合物,其中,所述组合物包含可可碱。
15.如上述权利要求中的任一项所述的组合物的单位剂量,其包含至少50mg总多酚。
16.如权利要求15所述的单位剂量,其具有小于500g的质量。
17.含有胺基的聚合物用于减轻或消除多酚的苦味和/或涩味的用途,其中,所述聚合物不是酪蛋白。
18.如权利要求17所述的用途,其中,至少部分所述多酚作为与所述聚合物的络合物存在。
19.如权利要求18所述的用途,其中,所述络合物是微粒形式。
20.一种制造如权利要求3至16中任一项所述的组合物的方法,其中,通过使所述聚合物和多酚在支持介质中接触而形成所述络合物。
21.一种制造包含多酚与含胺基聚合物的络合物的组合物的方法,该方法包括以下步骤:
i)混合所述多酚和聚合物,从而形成络合物;
ii)回收所述络合物;然后
iii)将所述络合物与支持介质组合。
22.如权利要求21所述的方法,其中,在步骤(ii)中回收作为微粒的络合物,并且其中,步骤(iii)包括在所述支持介质中分散该微粒。
23.如权利要求21或22所述的方法,其中,所述聚合物不是酪蛋白。
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PCT/EP2008/059024 WO2009016018A1 (en) | 2007-08-02 | 2008-07-10 | Compositions comprising polyphenol |
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EP (1) | EP2173186A1 (zh) |
JP (1) | JP2010535256A (zh) |
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-
2008
- 2008-07-10 WO PCT/EP2008/059024 patent/WO2009016018A1/en active Application Filing
- 2008-07-10 CN CN200880101437A patent/CN101778572A/zh active Pending
- 2008-07-10 EP EP08774986A patent/EP2173186A1/en not_active Withdrawn
- 2008-07-10 JP JP2010518599A patent/JP2010535256A/ja not_active Withdrawn
- 2008-07-10 EA EA201070215A patent/EA201070215A1/ru unknown
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WO2009016018A1 (en) | 2009-02-05 |
US20090035440A1 (en) | 2009-02-05 |
EA201070215A1 (ru) | 2010-08-30 |
JP2010535256A (ja) | 2010-11-18 |
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