CN102573513A - 作为脂溶性成分的乳化剂的新型植物胶-改性食物淀粉缀合物 - Google Patents
作为脂溶性成分的乳化剂的新型植物胶-改性食物淀粉缀合物 Download PDFInfo
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Abstract
本发明涉及基于植物胶和改性食物淀粉的新型缀合物及其制造方法,以及本发明涉及包含在基于这些缀合物的基质中的活性成分(优选脂溶性活性成分)和/或着色剂的组合物以及这些组合物的制造方法。
Description
本发明涉及基于植物胶和改性食物淀粉的缀合物及其制造方法,以及涉及包含在基于这些缀合物的基质中的活性成分(优选脂溶性活性成分)和/或着色剂的组合物以及这些组合物的制造方法。
本发明还涉及该发明的组合物用于对食物、饮料、动物饲料和/或化妆品组合物或药物组合物进行富集、强化、和/或着色的用途。
更具体地,本发明涉及含有一种或多种植物胶、一种或多种改性食物淀粉和一种或多种脂溶性活性成分和/或着色剂(尤其是类胡萝卜素)的组合物;用于制备这些组合物的方法;以及这些组合物作为添加剂用于对食物、饮料、动物饲料和/或化妆品组合物或药物组合物进行富集、强化和/或着色的用途。此外,本发明涉及含有上述组合物的食物、饮料、动物饲料、化妆品组合物或药物组合物。
用于对食物、饮料、动物饲料或化妆品组合物进行富集、强化、或着色的含有脂溶性活性成分(例如β-胡萝卜素)的组合物是本领域已知的。β-胡萝卜素由于其浓烈的以及对上述应用而言非常令人愉悦的橙色而是一种优选的着色剂化合物。因为最终的组合物通常是水性组合物如饮料,所以不得不向该组合物中添加额外的用于富集、强化和/或着色的化合物,以避免脂(油)相从产物中分离,这种分离会导致相应的产品不可接受。
因此,脂溶性活性成分通常与辅助化合物(如淀粉或鱼明胶)组合,从而在最终的水性组合物中避免相分离。然而,这些辅助化合物常对最终产物的颜色特性和/或营养特性具有负面影响。因此期望开发包含改进辅助化合物并且具有非常好性质(指组合物的颜色、味道、乳化、乳液稳定性和/或成膜能力)的新颖的脂溶性活性成分的组合物。此外,工业中存在如下的增长的需求:开发以天然来源的原料为基础的上述辅助化合物以替代明胶。
一种天然的水胶体——金合欢胶(gum acacia)(也称作阿拉伯胶(gumarabic))在饮料乳剂中被广泛用作乳化剂/稳定剂。它是高度溶于水的(以重量计多达50%),并且其水溶液提供乳液稳定性、包封能力和成膜能力。对金合欢树的茎和枝条施加压力时从中获得呈粘性渗出物的金合欢胶。金合欢胶从属于Leguminosae科的Acacia属的树中收集,这些树生长在非洲撒哈拉区域的若干国家中。该金合欢胶是属于糖蛋白类的天然大分子。它包括由鼠李糖和葡萄糖醛酸末端单元和四种糖(L-阿拉伯糖、L-鼠李糖、D-半乳糖、D-葡糖醛酸)构成的阿拉伯半乳聚糖多糖链,以及连接到该多糖链上的主要由氨基酸(OH-脯氨酸、丝氨酸、脯氨酸)构成的多肽链(Idris等人,Food Hydrocolloids,Part I to III,12,1998,379-388)。
Acacia Senegal(A.Senegal)是最常见的市售阿拉伯胶,也是最容易获得的胶质。其他可获得的胶质Acacia seyal(A.seyal)具有比Acacia Senegal更低的乳化特性,但是更便宜。然而,由于和物种、地理位置、土壤性质、气候和树龄相关的不相似的功能性,不同的批次间植物胶可能产生不均一的胶质性能。
WO2008110225公开了在介于100℃和115℃之间的温度下对金合欢胶进行热处理1至38小时以改善类胡萝卜素组合物的乳化性质的方法。然而,与使用这种金合欢胶缀合物制备的类胡萝卜素的颜色强度值和稳定性相关的性能保持非常大的可变性。
本文中使用的术语“改性食物淀粉”是指由通过已知的化学方法用疏水片段取代的淀粉所制成的改性淀粉。例如,淀粉可用环状二羧酸酐如琥珀酸酐和/或戊二酸酐处理,用烷基或烯基烃基取代。
改性食物淀粉通常用在现有技术中作为含有脂溶性活性成分和/或着色剂的组合物的基质,但是当用在饮料制剂中时缺乏长期稳定性。
另一方面,用于具体通过减少油滴尺寸来改善蛋白质的乳化性质和改善乳液稳定性的蛋白质-多糖缀合物也是本领域已知的。这种缀合物与未反应的蛋白质成分一起吸附在界面上,从而增强油滴间的空间稳定作用力。然而,在等电点周围的蛋白质-多糖缀合物的乳液稳定性不适于用在食物和饮料应用中,而且食物和饮料应用中的蛋白质乳化剂也是个问题。
因此,仍然需要新型的乳化物,这种新型的乳化剂在食物和饮料应用中用于制备对食物、饮料、动物饲料、化妆品组合物或药物组合物进行富集、强化和/或着色的并且不显示上述问题的脂溶性活性成分的组合物。
因此,本发明的一个目的是,确定新型的乳化剂并且提供具有上述所希望性质(例如改进的颜色强度和颜色稳定性以及在光学透明度和乳液稳定性方面的非常良好特性(如果适用的话))的脂溶性活性成分的组合物,而无需使用任何动物来源的产品。本发明的另一个目的是,例如通过使用新型的乳化剂来改进用于制备脂溶性活性成分的组合物的方法。
令人惊讶地发现,基于植物胶和改性食物淀粉的缀合物满足工业需求。
在本文中,术语“缀合物”是指通过通常需要加热的Maillard型反应来共价连接的高分子量聚合分子。它们通常由糖片段的反应性羰基和氨基酸中的亲核氨基之间的反应得到。缀合物通常具有如下特征:其分子量高于起始非缀合分子的分子量以及其形成稳定的聚合化学实体。
本发明的第一个目的是新型的植物胶-改性食物淀粉缀合物,其由如下组成:
a)一种或多种植物胶;
b)一种或多种改性食物淀粉,
其中当采用振荡流变测量(oscillatory rheological measurement)测定时,所述的经分离的植物胶-改性食物淀粉缀合物在水中的30wt%溶液在25℃下在1Pa的动态模量值下的相位角小于85度。
金合欢胶和/或茄替胶可以用作根据本发明的植物胶。最优选的植物胶是金合欢胶,包括例如源自一些非洲国家出产的Acacia Senegal属和/或Acacia Seyal属的胶。使用已经进行过处理(诸如纯化处理、脱盐处理、粉碎或喷雾干燥)植物胶也是可以的,对其水含量没有任何限制。此外,可以使用以块状、珠状、粗粒状、细粒状、小球状和粉末状(包括喷雾干燥粉末)形式获得的植物胶,没有任何偏好。
在优选的实施方式中,在本发明中使用源自Acacia Senegal的商购胶。
根据本发明,优选的改性淀粉是辛烯基琥珀酸钠淀粉(“OSA-淀粉”)。这些OSA-淀粉可含有其它水胶体,如淀粉、麦芽糖糊精、碳水化合物、胶质(gum)、玉米糖浆等,并可选地含有任何典型的乳化剂(作为共乳化剂),如脂肪酸甘油单酯和甘油二酯、脂肪酸的甘油多酯、卵磷脂、脱水山梨醇单硬脂酸酯和植物纤维或糖。OSA-淀粉以商品名HiCap100、Capsul、Capsul HS、Purity Gum 2000、UNI-PURE、HYLON VII等从例如National Starch商业获得;或从Roquette Frères商业获得;或以商品名C*EmCap从CereStar商业获得;或从Tate&Lyle商业获得。
用于表征植物胶-改性食物淀粉缀合物的平均分子量以克/摩尔(g/mol)表示,并且通过不对称流场流分级技术(asymmetric flow field flowfractionation)进行测定。不对称流场流分级技术(A4F)是一种单相色谱技术。对非常薄的流(flow)施加垂直作用力场,从而实现高分辨率的分离。
流和样品被限制在由两块通过间隔箔隔离的板构成的通道中。样品组成流出(elute),并且根据它们的尺寸进行分离(通过Brownian运动驱动的扩散),接着通过探测器阵列进行监测。最小的粒子较之最大的粒子以远远更快速地被运输通过通道。最小粒子的流出时间短于最大粒子的流出时间。这是与尺寸排除/凝胶渗透色谱(SEC/GPC)相比主要的不同,在尺寸排除/凝胶渗透平色谱中,最大的分子首先流出(IMM Beauvais,France,and Comprehensive Polymer Science,Vol 1,279页)。
根据本发明的植物胶-改性食物淀粉缀合物可以通过如下事实表征:它们的平均分子量与起始植物胶原料的平均分子量相比为至少1.2倍高;优选地,它们的平均分子量至少增加2倍,最优选至少增加3倍。作为例子,金合欢胶具有约3百万g/mol的平均分子量,而根据本发明的植物胶-改性食物淀粉缀合物的平均分子量为约1千万g/mol。
根据本发明的植物胶-改性食物淀粉缀合物还可以以它们在水性溶液(分离的缀合物的30%溶液)中的流变性质表征。可以采用同心圆筒几何结构(concentric cylinder geometry)(例如Mooney型或双间隙几何结构)实施稳态、振荡(动态)粘度测量。动态流变测量已确认了过滤通过500K Dalton隔膜(HOLLOW FIBER-GE Healthcare)的植物胶-改性食物淀粉缀合物的分子量增加并且分子量分布加宽。
根据本发明的过滤通过500K Dalton隔膜(HOLLOW FIBER-GEHealthcare)的植物胶-改性食物淀粉缀合物的水性溶液(33%w/w)展现与未缀合的胶质相比在25℃下至少1.2倍的增加粘度。
此外,植物胶-改性食物淀粉的分子结构可以由在25℃下30%水溶液的如实施例5中所述的相位角进行表征。根据本发明的植物胶-改性食物淀粉缀合物可以由如下事实进行表征:所述缀合物在1Pa的动态模量下具有小于85的相位角。更优选地,这些缀合物在1Pa的动态模量下的相位角小于82.5度、甚至更优选小于80度、最优选小于75度。
根据本发明的植物胶-改性食物淀粉缀合物的形式没有限制,其包括例如块状、珠状、粗粒状、细粒状、小球状或粉末状。
本发明的还一个目的是提供具有上述所需性质(例如在光学透明度和乳液稳定性方面的非常良好特性以及改进的颜色强度和颜色稳定性(如果适用的话))的脂溶性活性成分的组合物。
本发明的另一目的是一种组合物,该组合物包含a)10至70重量%的上述植物胶-改性食物淀粉缀合物;和b)0.1至60重量%的一种或多种脂溶性活性成分,各用量都是基于组合物的总重以干物质计。
根据本发明的组合物优选包含基于组合物的总重以干物质计的15至60重量%的植物胶-改性食物淀粉缀合物;和/或0.1至30重量%、还优选0.5至20重量%、最优选0.5至15重量%的一种或多种脂溶性成分,各用量都是基于组合物的总重以干物质计。
本文使用的术语“脂溶性活性成分”是指:选自由维生素A、D、E、K及其衍生物组成的组的维生素;多不饱和脂肪酸及其酯;亲脂性活性成分;类胡萝卜素;风味或芳香物质;以及它们的混合物。
根据本发明适合的多不饱和脂肪酸(PUFA)是单或多不饱和羧酸,其优选地具有16到24个碳原子,尤其是1到6个双键,优选地具有4或5或6个双键。
不饱和脂肪酸可属于n-6系列和n-3系列二者。n-3多不饱和酸的优选的例子是二十碳-5,8,11,14,17-五烯酸和二十二碳-4,7,10,13,16,19-六烯酸;优选的n-6多不饱和酸的例子是花生四烯酸和γ-亚麻酸。
多不饱和脂肪酸的优选衍生物是其酯,例如甘油酯,尤其是甘油三酯;尤其优选的是乙酯。n-3和n-6多不饱和脂肪酸的甘油三酯是特别优选的。
甘油三酯可含有3个一致的不饱和脂肪酸,或2或3个不同的不饱和脂肪酸。它们也可部分含有饱和的脂肪酸。
当衍生物是甘油三酯时,通常用甘油酯化三个不同的n-3多不饱和脂肪酸。在本发明的一个优选的实施方式中使用甘油三酯,其中30%的脂肪酸部分是n-3脂肪酸,且其中25%是长链不饱和脂肪酸。在进一步的优选的实施方式中,使用可商业获得的ROPUFA‘30’n-3Food Oil(DSMNutritional Products Ltd,Kaiseraugst,瑞士)。
在本发明的另一个优选的实施方式中,PUFA酯是ROPUFA’75’n-3EE。ROPUFA’75’n-3EE是乙酯形式的精制海产油(marine oil),其具有72%的n-3脂肪酸乙酯的最小含量。其用混合的生育酚、棕榈酸抗坏血酸酯、柠檬酸稳定,并含有迷迭香提取物。
在本发明的另一个优选的实施方式中,PUFA酯是ROPUFA′10′n-6Oil,其为具有最少9%γ-亚麻酸的精制的月见草油(evening primrose oil),用DL-α-生育酚和棕榈酸抗坏血酸酯稳定。
根据本发明,可以有利地使用含有多不饱和脂肪酸的甘油三酯的天然存在的油(一种或多种组份),例如海产油(鱼油)和/或植物油,也可以有利地使用从经发酵的生物质或经遗传修饰的植物中提取的油。
包含多不饱和脂肪酸甘油三酯的优选的油为橄榄油、葵花子油、月见草籽油、琉璃苣油(borage oil)、葡萄籽油、大豆油、花生油、小麦胚芽油(wheat germ oil)、南瓜子油、胡桃油、芝麻籽油、菜籽油(芥花籽)、黑加仑籽油(blackcurrant seed oil)、猕猴桃籽油、来自特定真菌的油和鱼油。
多不饱和脂肪酸的优选的例子为例如亚油酸、亚麻酸、花生四烯酸、二十二碳六烯酸、二十碳五烯酸等等。
根据本发明,优选的亲脂性活性成分是:白藜芦醇;藁本(ligusticum);选自辅酶Q10(也称作“Q10”)、辅酶Q9和/或其还原形式(相应的泛醇)的泛醌和/或泛醇(一种或多种组分);染料木黄酮和/或α-硫辛酸。
根据本发明,优选的脂溶性活性成分为类胡萝卜素,特别是β-胡萝卜素、番茄红素、叶黄素、胭脂树橙(bixin)、虾青素、阿朴胡萝卜素醛、β-阿朴-8′-胡萝卜素醛、β-阿朴-12′-胡萝卜素醛、角黄素、隐黄素、柠檬黄质和玉米黄素。最优选的是β-胡萝卜素。
此外,本发明的组合物可(还)含有一种或多种选自单糖、二糖、寡糖和多糖的赋形剂和/或佐剂,水溶性抗氧化剂和脂溶性抗氧化剂。
本发明组合物中可存在的单糖和二糖的例子是蔗糖、转化糖、木糖、葡萄糖、果糖、乳糖、麦芽糖、食糖和糖醇。
寡糖和多糖的例子是淀粉,淀粉水解产物例如糊精和麦芽糖糊精,特别是具有5到65葡糖当量(DE)的那些,和葡萄糖浆,特别是具有20到95DE的那些。术语“葡糖当量”(DE)表示水解程度,是以干重为基础以D-葡萄糖计的还原糖的量的量度;该标度以DE接近0的天然淀粉和DE为100的葡萄糖为基础。优选地,在根据本发明的组合物中使用麦芽糖糊精。
水溶性抗氧化剂可例如是抗坏血酸或其盐,优选地为抗坏血酸钠,水溶性多酚例如羟基酪醇和橄榄苦苷、苷元、表没食子儿茶素没食子酸酯(EGCG)或迷迭香或橄榄的提取物。
脂溶性抗氧化剂可例如是生育酚,例如dl-α-生育酚(即合成的生育酚)、d-α-生育酚(即天然生育酚)、β-生育酚或γ-生育酚,或其两种或更多的混合物;丁基化的羟基甲苯(BHT);丁基化的羟基茴香醚(BHA);乙氧基喹啉,没食子酸丙酯;叔丁基羟基喹啉;或6-乙氧基-1,2-二羟基-2,2,4-三甲基喹啉(EMQ),或脂肪酸的抗坏血酸酯,优选地为棕榈酸抗坏血酸酯或硬脂酸抗坏血酸酯。
根据本发明的组合物优选包含小于30重量%、进一步优选小于10重量%、进一步优选小于3重量%的油(基于组合物的总重以干物质计)。最优选地,组合物不包含任何油。
本文上下文中使用的术语“油”包括适用于组合物的期望用途的任何甘油三酯或任何其他油(例如萜)。甘油三酯适当地是植物油或脂肪,优选地为玉米油、葵花子油、大豆油、红花油、菜籽油、花生油、棕榈油、棕榈仁油、棉籽油、橙油、柠檬烯、橄榄油或椰子油。
固体组合物可额外含有抗结块剂,例如硅酸或磷酸三钙等等,并且至多为10重量%,优选地为0.1到5重量%,分别基于组合物的总重以干物质计。
此外,组合物可以包含水。
在本发明的另一方面中,植物胶-改性食物淀粉缀合物的制造包括如下步骤:
I)分别将植物胶和改性食物淀粉二者悬浮在水中;
II)可选从悬浮的改性食物淀粉中除去未溶解的材料;
III)以1∶1至20∶1的比例将步骤I)的植物胶的水性溶液混入步骤I)和可选步骤II)制备的改性食物淀粉的水性溶液中,并且将所得混合物搅拌约1小时;
IV)可选地,在室温下孵育步骤III)的混合物1至24小时;
V)将步骤IV)的混合物干燥以除水并且生产粉末;
VI)将步骤V)的所得粉末在50℃至150℃之间加热1至72小时,从而形成植物胶-改性食物淀粉缀合物。
步骤VI)的植物胶-改性食物淀粉缀合物可以原样使用、在例如干燥器中干燥待用、或者可选根据如下步骤进一步纯化(例如为了表征缀合物):
VII)可选地,将步骤VI)的植物胶-改性食物淀粉缀合物悬浮在水中;
VIII)可选地,使水性溶液通过500k Dalton隔膜(HOLLOW FIBER-GE Healthcare)进行渗滤(diafiltration),直到稀释体积(Vd)至少大于或等于4(Vd=透过的液体体积/初始加料的体积);
IX)将步骤VIII)的混合物干燥以除水并且生产粉末。
这个过程在实施例1中举例说明。优选的植物胶的水性溶液包含8%w/w的金合欢胶,但并不局限于这个浓度。优选的改性食物淀粉的水性溶液是30%w/w溶液,但并不局限于这个浓度。植物胶与改性食物淀粉的优选重量比被选择在1∶1至20∶1的范围内,进一步优选的重量比被选择在3∶2至4∶1的范围内,进一步优选的重量比被选择在13∶7至3∶1的范围内,进一步优选的重量比被选择在2∶1至5∶2的范围内。
步骤V)混合物的干燥可以通过喷雾干燥进行以便保持低于8%的水含量。
步骤VI)最好通过在100至120℃之间加热12至72小时来进行,但是温度可以在50至150℃之间,而且时间可以在1至72小时之间。
在另一优选的实施方式中,本发明涉及用于制造一种组合物的方法,所述组合物包含上述植物胶-改性食物淀粉缀合物,还包含一种或多种脂溶性成分。这个方法包括如下步骤:
I)将适当量的可通过上述方法得到的植物胶-改性食物淀粉缀合物分散在适当量的水中;
II)将一种或多种脂溶性活性成分添加到步骤I)制备的溶液中;
III)采用本领域技术人员已知的常规乳化方法对步骤II)的混合物进行乳化;
IV)可选地,干燥步骤III)的乳液。
这个方法根据已在WO 2008110225中描述的方法进行。
本发明还涉及上文所述的组合物用于对食物、饮料、动物饲料和/或化妆品组合物进行富集、强化和/或着色的用途,优选用于对饮料进行富集、强化和/或着色的用途。
本发明的其他方面是包含上文所述的组合物的食物、饮料、动物饲料、化妆品。
其中可使用本发明的产物形式作为着色剂或添加剂成分的饮料可以是碳酸饮料,例如调味的塞耳特斯水(flavored seltzer water)、软饮或矿物饮品,以及非碳酸饮料,例如调味的水、果汁、水果宾治(fruit punches)和这些饮料的浓缩形式。它们可以基于天然的水果汁或蔬菜汁或基于人工香料。还包括在内的是酒精饮料和速溶饮料粉(instant beverage powder)。另外,还包括含糖饮料、不含热量并含有人工甜味剂的减肥饮料(dietbeverage)。
另外,得自天然或合成来源的乳制品也属于食物制品的范围,其中本发明的产物形式可被用于其中作为色剂或添加剂成分。这类制品的典型例子是乳饮品、冰激凌、乳酪、酸乳等等。乳替代制品如豆浆饮品和豆腐制品也包括在该应用范围内。
还包括在内的是包含本发明的产物形式作为着色剂或添加剂成分的甜品(sweets),如糖果制品(confectionery product)、糖果、口香糖、甜点,例如冰激凌、果冻(jellies)、布丁、即食布丁粉等等。
还包括在内的是谷物、点心、曲奇、意大利面(pasta)、汤和沙司(sauces)、蛋黄酱、沙拉酱等等,其含有本发明的产物形式作为着色剂或添加剂成分。另外,用于乳和谷物的水果制备物也包括在内。
经由本发明的组合物添加至食物制品中的一种或多种脂溶性活性成分、优选类胡萝卜素、具体β-胡萝卜素的终浓度基于食物组合物的总重可优选0.1到50ppm,尤其是1到30ppm,更优选3到20ppm,例如约6ppm,并取决于有待着色或强化的具体食物制品和着色或强化的预期等级。
优选地通过以本发明组合物的形式向食物制品中添加脂溶性活性成分,来获得本发明的食物组合物。为了食物或药物制品的着色或强化,可根据本身已知的应用可分散于水中的固体制品形式的方法,使用本发明的组合物。
通常,组合物可作为水性浓缩溶液形式添加,或者作为与适用于特定应用的其他食物成分的干粉混合物或预混合物添加。根据最终应用的配方,可例如使用干粉搅拌器、低剪力混合器、高压匀化器或高剪力混合器完成混合。显而易见的是,这类技术是本领域技术人员已知的。
本发明还通过以下的实施例进一步阐述,所述实施例不是要限制本发明的范围。
实施例
实施例1:金合欢胶-OSA淀粉缀合物的制备
向金合欢胶的水性溶液(8%w/w)中添加OSA淀粉的水性溶液(30%w/w)。将混合物在室温下混合1小时,然后使其静置过夜以便完全水合。第二天,喷雾干燥产物(Nitro-Mobile Minor TN“2000”-T入口:180℃;T出口:75℃)。然后,将收集的粉末转移到两升的广口瓶中,并且在110℃的烘箱中加热20小时并储存在干燥器中。
制备如下缀合物:表1
实施例2:金合欢胶-OSA淀粉缀合物的纯化
将每种金合欢胶-OSA淀粉缀合物的水性溶液(8至10%w/w)通过分子量截止为500KDa的中空纤维隔膜(GE Healthcare-Type UFP-500-E-6A)以1bar的TMP采用连续渗滤进行过滤。该过程在透过液的糖水平低到无法检测到(UV测量)时终止。最后喷雾干燥留下的溶液(Nitro-MobileMinor TN“2000”-T入口:180℃;T出口:75℃),并且储存并使用收集的产物无需进行任何进一步的修饰。
实施例3:通过IMM-Beauvais,France所进行的不对称流场流分级技术进行分子量的测量来表征金合欢胶-OSA淀粉缀合物
技术细节:
流出缓冲液:超高品质水(UHQ-双重去矿物,在0.2μm过滤,UV处理)
在线过滤器类型:0.1μm,改性纤维素
分级系统:WYATT ECLIPSE 3
多角激光散射测量:658nm
折射率测量:658nm,dn/dc=0.19ml/g
UV Agilent 1200系列:280nm
所用超滤膜:再生纤维素,截止10kDa
间隔的厚度:250μm
分级单元的长度:13cm(SCELL)
注射前的样品处理:将样品在室温下溶解在UHQ水中过夜。然后,直接注入样品而没有任何过滤。
表2:通过不对称流场流分级测量的植物胶-OSA淀粉缀合物的平均分子量
样品 | 回收率(%) | 平均分子量(g/mol) |
金合欢胶 | 93.7 | 3.0x106 |
金合欢胶-OSA淀粉1∶1 | 89.8 | 1.2x107 |
金合欢胶/OSA淀粉7∶3 | 91.2 | 1.1x107 |
金合欢胶/OSA淀粉9∶1 | 92.3 | 8.2x106 |
金合欢胶/OSA淀粉19∶1 | 92.6 | 8.7x106 |
高回收值表示产品在注入前良好溶解,并且在柱子上的分离和探测良好。该高回收值可能与方法的良好重复性相关联。
实施例4:通过粘度表征金合欢胶-OSA淀粉缀合物
业已利用TA Instrument AR-G2应力受控流变仪采用同心圆筒几何结构(Mooney)对各个金合欢胶-OSA淀粉缀合物的水性溶液(33%w/w)进行各种粘度测量。
结果示于表3中:各实体的粘度值采用20s-1的剪切速率在25℃下测定。
表3:对未分离的金合欢胶-OSA淀粉缀合物或者对根据可选步骤VII)至IX)的分离材料进行的粘度测量结果的汇总
实施例5:金合欢胶-OSA淀粉缀合物的水性溶液的流变测量结果
在25℃下测定分离的缀合物在水中的30wt%溶液的动态流变特性。业已采用安装有双间隙几何结构的TA Instruments AR-G2流变仪实施振荡测量。所谓的频率扫描在628弧度/s和0.628弧度/s之间以递减次序以每十进位5个频率形式进行。该仪器以受控应变模式运行,其中所施加变形的幅度被固定为10%。
该仪器产生了动态流变特性的数据,这些数据可以以各种格式表示,并且可以容易相互转化。从频率依赖性的存储模量G’(ω)和损耗模量G”(ω)开始,建立如下方程(J.D.Ferry,‘Viscoelastic Properties of Polymers’,JohnWiley&Sons,(1980)3rd Edition):
动态模量Gd(ω)=(G’(ω)2+G”(ω)2)0.5
相位角δ=arctan(G”(ω)/G’(ω))
动态粘度η(ω)=Gd(ω)/ω
图1示出了动态粘度η与角频率ω之间的关系。在高于250弧度/s的频率下获得的数据由于动态测量用双间隙几何结构的高惯性而被认为是不可靠的。
图1:阿拉伯胶材料的动态粘度与频率的函数关系。GA=未经改性的阿拉伯胶;GA CL=阿拉伯胶交联48小时;GA-OSA 1/1=以1/1比率制备的阿拉伯胶-OSA淀粉缀合物;GA-OSA 7/3=以7/3比率制备的阿拉伯胶-OSA淀粉缀合物;GA-OSA 9/1=以9/1比率制备的阿拉伯胶-OSA淀粉缀合物;GA-OSA 19/1=以19/1比率制备的阿拉伯胶-OSA淀粉缀合物;EM10=来自San-Ei Gen F.F.I的Super Gum EM 10”。
材料的流变行为主要是牛顿流体的流变行为(表现出几乎与频率无关的粘度)。然而,少数材料在低于10弧度/s的频率下显示清晰的粘度的增长,这归因于存在弹性/凝胶状级分。
通常利用溶液粘度作为溶解聚合物的分子量指标。在这个情况下,我们将在10弧度/s的角频率下的动态粘度(η)定义为溶解的金合欢胶聚合物的摩尔质量指标(Mwt)。这个频率的选择排除了如果存在的凝胶级分对摩尔质量指标的影响。这样得到了以下材料分子量的排序:Mwt GA<GA-OSA 1/1≤GA-OSA 19/1<GA CL<GA-OSA 9/1<EM10<GA-OSA 7/3
为了得到更详细的关于材料的分子结构的信息,相位角δ与动态模量Gd(ω)的关系图示于图2中。同样,也从这项分析中排除了在高于250弧度/s的频率下测定的数据。
图2:各种阿拉伯胶材料的相位角与动态模量之间的关系。GA=未经改性的阿拉伯胶;GA CL=阿拉伯胶交联48小时;GA-OSA 1/1=以1/1比率制备的阿拉伯胶-OSA淀粉缀合物;GA-OSA 7/3=以7/3比率制备的阿拉伯胶-OSA淀粉缀合物;GA-OSA 9/1=以9/1比率制备的阿拉伯胶-OSA淀粉缀合物;GA-OSA 19/1=以19/1比率制备的阿拉伯胶-OSA淀粉缀合物;EM 10=来自San-Ei Gen F.F.I的Super Gum EM 10”。
在最高的模量值(Gd=30-100Pa)下,溶液的流变特性主要由溶解的聚合链决定。在特定的动态模量值下的较小相位角表示较宽的分子量分布或者存在长链支化分子(Trinkle,S.,and Freidrich,C.Rheologica Acta,(2001)40(4),pp.322-328)。例如GA-OSA 7/3材料的情况是后者。我们将在固定的100Pa的动态模量值下的相位角值定义为溶解的聚合物的分子量分布(PD)宽度的指标。这个相位角值可以通过对δvs.Gd关系图以线性对数坐标内推或外推来得到。
PD GA<GA-OSA 1/1<GA CL<EM 10<GA-OSA 19/1<GA-OSA 9/1<GA-OSA 7/3
此外,在低动态模量值下的相位角可被用作弹性/凝胶状级分存在与否的指标。在存在(永久)弹性级分的情况下,相位角随着动态模量的下降而大幅下降。较低的相位角值表示存在较多的凝胶。我们使用在1Pa的动态模量下的相位角值作为材料中存在的凝胶量的指标,前提条件是:随着动态模量下降低于10Pa,相位角显示大于1度的下降。这样得到了如下凝胶级分(GF)的排序:
GF EM 10<GA<GA-OSA 1/1<GA CL
其他材料没有显现存在凝胶的流变特性,这是因为相位角并未随着动态模量的下降而下降。然而,样品GA-OSA 7/3在Gd=1Pa下显示远远更低的相位角值,这归因于存在高分子量、可能长链支化的聚合链。
结论
图1和图2给出的结果因此表明:
-阿拉伯胶中存在少量的凝胶级分。
-从阿拉伯胶到加热48小时的阿拉伯胶(CL)分子量递增,同时其分子量分布加宽,并且凝胶级分显著增加。
-与不显现凝胶级分的金合欢胶相比,GA-OSA 19/1和GA-OSA9/1植物胶-改性食物淀粉缀合物的分子量增加。
-GA-OSA 7/3植物胶-改性食物淀粉缀合物的分子量甚至更明显的增加,同时其分子量分布显著加宽,这可能是因为存在长链支化分子。不能探测到凝胶级分的存在。
-与GA-OSA 19/1、GA-OSA9/1和GA-OSA7/3缀合物相比,GA-OSA1/1植物胶-改性食物淀粉缀合物的分子量分布较窄,同时存在凝胶状级分。然而,与GA和GA-CL相比,该凝胶级分具有较短的松弛时间(relaxation time)。
-最后,与GA相比,EM 10材料具有较高的分子量,同时具有如缀合物般的较宽分子量分布。存在非常少的凝胶级分,然而远远少于未改性的GA。
实施例6:制备含有β-胡萝卜素的金合欢胶-OSA淀粉缀合物
在广口瓶中,将基于胶质的缀合物—金合欢胶/OSA淀粉1∶1倒入水中并且在室温下搅拌,直到其完全溶解。与此同时,将含有β-胡萝卜素、玉米油、dl-α-生育酚溶解在溶剂中。然后,将有机相添加到水性相中,并使所得混合物乳化(FLUID 5000RPM)。最后,在减压下蒸发溶剂。所得产物通过粉末捕捉剂(powder catch)(在淀粉床中)转化成干燥形式。
表4:含有β-胡萝卜素的金合欢胶-OSA淀粉缀合物
组分 | 量(wt%) |
金合欢胶-OSA淀粉缀合物 | 58.75 |
β-胡萝卜素 | 4.7 |
dl-α-生育酚 | 1.42 |
玉米油 | 5.12 |
粉末捕捉剂 | 30 |
实施例7:制备含有生育酚乙酸酯的金合欢胶-OSA淀粉缀合物
在反应器中,将基于胶质的缀合物(金合欢胶-OSA淀粉)和麦芽糊精先后倒入水中并且在室温下搅拌,直到完全溶解。此后,将事先温热至60℃的生育酚乙酸酯添加到水性相中。然后使所得混合物乳化(FLUID5000RPM)。最后,通过喷雾干燥,将所得产物转化成干燥形式。
表5:含有生育酚乙酸酯的金合欢胶-OSA淀粉缀合物
组分 | 量(wt%) |
金合欢胶-OSA淀粉缀合物 | 30 |
dl-α-生育酚乙酸酯 | 50 |
麦芽糊精 | 19 |
二氧化硅 | 1 |
Claims (13)
1.一种植物胶-改性食物淀粉缀合物,其由如下组成:
a)一种或多种植物胶;
b)一种或多种改性食物淀粉,
其中当采用振荡流变测量测定时,所述的经分离的植物胶-改性食物淀粉缀合物在水中的30wt%溶液在25℃下在1Pa的动态模量值下的相位角小于85度。
2.根据权利要求1的植物胶-改性食物淀粉缀合物,其特征在于所述胶是金合欢品种Acacia Senegal胶。
3.根据权利要求1或2的植物胶-改性食物淀粉缀合物,其特征在于所述改性食物淀粉是辛烯基-琥珀酸盐淀粉。
4.一种组合物,其包含:
a)10至70重量%的根据权利要求1至3中任意一项的植物胶-改性食物淀粉缀合物;和
b)0.1至60%的一种或多种脂溶性活性成分。
5.根据权利要求4的组合物,其特征在于所述脂溶性活性成分(一种或多种化合物)选自维生素A、D、E、K及其衍生物;多不饱和脂肪酸及其酯;亲脂性健康成分;类胡萝卜素;风味或芳香物质;以及它们的混合物。
6.根据权利要求4或5的组合物,其特征在于所述脂溶性活性成分(一种或多种化合物)为类胡萝卜素,特别是β-胡萝卜素、番茄红素、叶黄素、胭脂树橙、虾青素、阿朴胡萝卜素醛、β-阿朴-8′-胡萝卜素醛、β-阿朴-12′-胡萝卜素醛、角黄素、隐黄素、柠檬黄质和/或玉米黄素。
7.根据权利要求4至6中任一项的组合物,其特征在于所述组合物还包含一种或多种佐剂和/或赋形剂。
8.一种用于制备权利要求1至3中任一项的植物胶-改性食物淀粉缀合物的方法,其包括如下步骤:
I)分别将植物胶和改性食物淀粉二者悬浮在水中;
II)可选从悬浮的改性食物淀粉中除去未溶解的材料;
III)以1∶1至20∶1的比例将步骤I)的植物胶的水性溶液混入步骤I)和可选步骤II)制备的改性食物淀粉的水性溶液中,并且将所得混合物搅拌约1小时;
IV)可选地,在室温下孵育步骤III)的混合物1至24小时;
V)将步骤IV)的混合物干燥以除水并且生产粉末;
VI)将步骤V)的所得粉末在50℃至150℃之间加热1至72小时,从而形成所述植物胶-改性食物淀粉缀合物;
VII)可选地,将植物胶-改性食物淀粉缀合物悬浮在水中;
VIII)可选地,使水性溶液通过500k Dalton隔膜(HOLLOW FIBER-GE Healthcare)进行渗滤,直到稀释体积(Vd)至少大于或等于4;并且
IX)将步骤VIII)的混合物干燥以除水并且生产粉末。
9.一种用于制备权利要求4至6中任一项的组合物的方法,所述方法包括如下步骤:
I)将适当量的根据权利要求1至3中任一项的植物胶-改性食物淀粉缀合物分散在适当量的水中;
II)将一种或多种脂溶性活性成分添加到步骤I)制备的溶液中;
III)采用本领域技术人员已知的常规乳化方法对步骤II)的混合物进行乳化;
IV)可选地,干燥步骤III)的乳液。
10.根据权利要求8所能得到的植物胶-改性食物淀粉缀合物。
11.权利要求5至7中任一项的组合物用于对食物、饮料、动物饲料、化妆品组合物或药物组合物进行富集、强化和/或着色的用途。
12.一种通过将权利要求5至7中任一项的组合物与其他常用的饮料成分进行混合来制造饮料的方法。
13.根据权利要求12的方法所能得到的饮料。
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US20180177214A1 (en) * | 2015-06-12 | 2018-06-28 | Dsm Ip Assets B.V. | New orange color for edible coatings |
WO2016198570A1 (en) * | 2015-06-12 | 2016-12-15 | Dsm Ip Assets B.V. | New natural color for edible coatings |
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MY193047A (en) | 2016-04-01 | 2022-09-26 | Dsm Ip Assets Bv | Tablettable formulation comprising milled carotenoid |
PL3435786T3 (pl) | 2016-04-01 | 2020-12-14 | Dsm Ip Assets B.V. | Napoje zawierające stabilne granulki mielonej luteiny |
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