CN102186886B - 新型聚葡萄糖材料 - Google Patents
新型聚葡萄糖材料 Download PDFInfo
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- CN102186886B CN102186886B CN200980142399.4A CN200980142399A CN102186886B CN 102186886 B CN102186886 B CN 102186886B CN 200980142399 A CN200980142399 A CN 200980142399A CN 102186886 B CN102186886 B CN 102186886B
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- Prior art keywords
- dextrose
- acid
- poly
- sugar
- weight
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- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000001259 polydextrose Substances 0.000 title claims abstract description 107
- 235000013856 polydextrose Nutrition 0.000 title claims abstract description 107
- 229940035035 polydextrose Drugs 0.000 title claims abstract description 107
- 229920001100 Polydextrose Polymers 0.000 title abstract description 20
- 239000000463 material Substances 0.000 title description 15
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
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- 235000000346 sugar Nutrition 0.000 claims description 22
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Classifications
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- A23G1/32—Cocoa products, e.g. chocolate; Substitutes therefor characterised by the composition containing organic or inorganic compounds
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- A—HUMAN NECESSITIES
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- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
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- A—HUMAN NECESSITIES
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- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/02—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation containing fruit or vegetable juices
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, 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
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- A—HUMAN NECESSITIES
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- A23L—FOODS, 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
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Abstract
本发明公开了一种新型的水溶性聚葡萄糖。这种新型的聚葡萄糖包含至少75%重量的具有5或更大的聚合度(DP)的糖分子,特征为不可消化的纤维含量为至少80%重量。而且,本发明涉及制备此种新型聚葡萄糖的方法以及此种聚葡萄糖在例如食物产品、药物产品和个人护理产品的产品中的用途。
Description
技术领域
本发明涉及一种新型水溶性聚葡萄糖。这种新型聚葡萄糖包含增加量的具有较高的聚合度(DP)的糖分子并具有高的不可消化纤维含量。而且,本发明涉及制备此种新型聚葡萄糖的方法和此种新型聚葡萄糖在例如食物产品、药物产品和个人护理产品的产品中的用途以及包含此种聚葡萄糖的产品。
发明背景
酸催化的糖的聚合反应为公知的现象,这描述于多种常规的文章、书和专利中。
聚葡萄糖为市售可得且所有这些聚葡萄糖产品都包含多种对味道、颜色和热量值有贡献的残留化合物,例如葡萄糖、山梨醇、柠檬酸和其他化合物。低分子量化合物例如1,6-葡糖酐和5-羟甲基糠醛引起苦味和臭味。
US 3,766,165公开了用作低热量食物成分的聚合物可通过将右旋糖或麦芽糖,任选与少量的多元醇,在可食用的聚羧酸催化剂存在时减压加热来制备。US 3,876,794公开了多种包含同样物质的食物。
紧跟这种重要的公开之后,进一步的开发和研究集中于克服US3,766,165和US 3,876,794的产品中出现的酸和/或苦味。
例如,WO 98/41545公开了通过使葡萄糖或含葡萄糖的材料与多元醇在无机酸例如磷酸、盐酸和/或硫酸存在下反应制备多糖的方法。依照此公开,如其中建议的低水平的催化剂使得反应过程中产生最小的臭味或无臭味和几乎没有颜色形成。该文献中公开的方法可包含进一步的纯化方法。
US 5,831,082描述了通过分离获得高纯水溶性聚葡萄糖的方法。报道的超过99.2%水溶性聚葡萄糖包含相当大量的二-、三-和四糖。据报道此公开的产品没有苦的余味。
US 5,051,500描述了制备无规结合的多糖的连续的方法。
US 2004/0038837涉及麦芽糖糊精(此处也称为聚葡萄糖)与蔗糖组合以引起双相液体形成的用途。上述产品具有4至22的聚合度并以MaltrineTM出现在市场,其符合麦芽糖糊精类产品。
EP 0 458 748描述了基本没有苦味和颜色的聚葡萄糖组合物。实施例1中将聚葡萄糖溶液加入至阴离子交换器。洗脱液(含聚葡萄糖)不含柠檬酸,但是仍存在较低分子量杂质例如1,6-葡糖酐、山梨醇和葡萄糖。
US 5,831,082描述了获得高纯的水溶性聚葡萄糖的方法。含有0.5至3%柠檬酸的粗聚葡萄糖通过使用应用强酸性胶的模拟的移动床系统进行纯化。DP6+馏分总是为约56-58%重量。
考虑到现有技术,对于改善的水溶性聚葡萄糖材料仍有相当大的需求,该材料包含增加量的具有较高聚合度的糖分子和减少量的可消化的单-和寡糖。本发明提供了此种新型的聚葡萄糖。
发明概述
本发明涉及含有至少75%重量的具有5或更大的聚合度的糖分子的新型水溶性聚葡萄糖。更优选地,该聚葡萄糖含有至少80%重量的具有5或更大的聚合度的糖分子,且特征为不可消化的纤维含量为至少80%重量,优选至少85%重量,更优选至少90%重量。而且,本发明提供了制备此类聚葡萄糖的方法,该方法包括以下步骤:
a)提供粗聚葡萄糖,
b)将pH调节至6至8,优选约7,和
c)色谱分离成至少两种馏分,其中一种馏分富含具有1至4的聚合度的糖分子而另一种馏分富含本发明所述的新型水溶性聚葡萄糖。
而且,本发明涉及该新型聚葡萄糖在制备例如食物产品、药物产品和个人护理产品的产品中的用途并涉及所述含有该聚葡萄糖的食物产品、药物产品和个人护理产品。
发明详述
本文所指的聚葡萄糖为水溶性的填充剂(bulking agent)。它为无规交联的(分支的)葡聚糖聚合物(多糖),其特征为主要具有β-1-6和β-1-4键,且其通过糖的单独或在糖醇存在下的酸催化的缩合制成。聚葡萄糖本质上不同于麦芽糖糊精,麦芽糖糊精通过淀粉材料水解获得,且它包含大量的α-1-4键。
本发明的新型聚葡萄糖为具有增加量的具有5或更大的聚合度(DP)的糖分子的聚葡萄糖。聚合度具有聚合物化学中的含义,指链中重复单元的数量。聚合度为分子量的量度且单体的分子量以约162计算。该增加量的具有5或更大的DP的糖分子为至少75%重量且更优选,至少80%重量。该新型聚葡萄糖进一步的特征为,不可消化的纤维含量为至少80%重量,优选至少85%重量,更优选至少90%重量。不可消化纤维在小肠中既不被消化也不被吸收。它具有至少一种以下性质:增加粪便产生、刺激结肠发酵、减少空腹胆固醇水平和/或减少的餐后血糖和/或胰岛素水平。不可消化纤维通过在37℃和pH6使用新鲜的透析的大鼠小肠粉测定。
一个优选的实施方案中,本发明的聚葡萄糖还包含少于20%的具有1至4的DP的糖分子(单体和寡聚体),且优选这些单体和寡聚体的量少于15%重量,更优选少于10%重量。关于本发明,术语“寡聚体”和“寡糖”用于描述那些具有1至4的DP的聚合反应的产物,即它们包含1至4个对应于糖或糖醇单元的部分,例如4个糖单元或3个糖和1个糖醇单元,彼此通过共价键例如糖基键连接。与此相反,那些得自聚合反应的具有5或更大的聚合度的分子被称为“聚合物”或“多糖”。如果包含葡萄糖或其他己糖的反应物用于该聚合反应,那么这些聚合物具有约828g/mol或更高的分子量。
此外,本发明的聚葡萄糖具有低于2.0,或优选低于1.8的描述摩尔质量分布的分散的分子量分散度。同义的术语为多分散性。这是重均分子量与数均分子量的比。
本发明还涉及通过小于60μm,优选小于55μm,且更优选小于50μm的体积平均直径表征的本发明的聚葡萄糖。体积平均直径的计算基于分布的矩(moment)的定义,并且在ISO/FDIS 9276-2中给出实例。
最后,依照本发明,所述聚葡萄糖为低热量的,且非生龋的。其非生龋性由体外试验测定。
本发明的另一实施方案涉及制备上文限定的新型聚葡萄糖的方法,所述方法包括以下步骤:
a)提供粗聚葡萄糖;
b)将步骤a)的粗聚葡萄糖的pH调节至6至8,优选约7,例如通过加入碱性化合物;和
c)将步骤b)的产物色谱分离成至少两种馏分,其中一种馏分富含具有1至4的DP的糖分子,另一种馏分富含含有至少75%的具有5或更大DP的分子的聚葡萄糖。
一个实施方案中,本发明的方法通过糖的酸催化的聚合提供了步骤a)的粗聚葡萄糖。
用于该方法的第一步的糖优选为葡萄糖和含葡萄糖的糖。这些糖可为葡萄糖(右旋糖)、麦芽糖、淀粉水解产物等,其中糖部分的馏分还可用羧酸酯化。这些糖可以以无水的或水合的状态使用,或者它们可在水溶液中使用。
任选地,用作原材料的糖还可包含糖醇。优选用于原材料的糖醇的量为聚合反应物(糖)的0至20%重量。这些糖醇可包含丙三醇、赤藓醇、苏糖醇、戊糖醇(如木糖醇)和己糖醇(如山梨醇、甘露醇或半乳糖醇)的一种或多种。优选的糖醇包含一种或多种己糖醇且特别是山梨醇。
多种酸可用于催化聚合反应以获得步骤a)的粗聚葡萄糖。优选的这些催化剂为能够消耗的酸以减少原本为检查催化剂酸存在并且,如有必要,从最终产物将其去除的必要的控制和成本。特别是,优选的酸为可食用的酸(食品级酸)例如磷酸、柠檬酸、苹果酸、琥珀酸、己二酸、葡糖酸、酒石酸、富马酸及其混合物。特别优选的是柠檬酸和/或磷酸。用作催化剂的酸的量应为低于相对于用于聚合反应的糖(和多元醇,如果存在)原材料的量的10%摩尔。优选该量应为明显低于该水平,例如至多3、至多1、至多0.5、至多0.1%摩尔或更低。
粗聚葡萄糖仍含有用于聚合反应的残留酸。
步骤b)中,通过加入碱性化合物使粗聚葡萄糖的pH增加至6至8,优选约7。令人惊奇的是,已发现通过增加pH在随后的分离步骤中任何降解产物例如呋喃、糠醛和5-羟甲基糠醛(5HMF)的形成均被防止。优选通过加入液体碱性化合物,例如溶于水的氢氧化钠或其他本领域已知的合适的碱化化合物增加pH。
步骤c)的色谱分离产生至少两种馏分,其中一种馏分与步骤b)之后的粗聚葡萄糖比较富含单-和寡糖分子,即该馏分富含右旋糖、麦芽糖和其他寡聚物(至多DP4);而另一种馏分与步骤b)之后的粗聚葡萄糖相比富含多糖(优选有5和更高的聚合度)。
优选色谱分离在阳离子交换树脂(例如强酸性阳离子(SAC)交换树脂)上进行。
最后,本发明的聚葡萄糖不含降解产物(例如呋喃、糠醛和5-羟甲基糠醛(5HMF))并且经色谱分离得到一种新的聚合度分布型(profile)并且最终产物为低热量的、非生龋的且具有至少80%的不可消化的纤维含量。
本发明另一方面涉及包含至少75%重量的具有5或更大的DP的糖分子且特征为不可消化的纤维含量为至少80%重量的聚葡萄糖在制备选自食物产品、药物产品和个人护理产品的产品中的用途。本发明的另一方面还涉及包含此种新型聚葡萄糖的食物产品、药物产品和个人护理产品。这些产品中,包含至少75%重量糖聚合物且特征为不可消化的纤维含量为至少80%重量的聚葡萄糖可以与常规聚葡萄糖一起或代替常规聚葡萄糖使用。
本发明的药物产品包括片剂、用于制备片剂的赋形剂、用于糖浆或其他液体或粘性流体的粘度剂、溶液、乳液或悬液。
本发明的个人护理产品选自流体、半流体或固体产品例如牙膏、漱口液等。
本发明的聚葡萄糖可被用作湿润剂。湿润剂为主要用于食物和化妆品产品以帮助保湿的物质。
本发明的聚葡萄糖特别可用于制备食物产品。这些食物产品包括特别是糖食、焙烤产品、饮料和奶产品(diary product)。
在本发明范围内的甜食组合物包括巧克力、晶体和非晶体产品。在本发明范围内的非晶体产品包括硬糖果、薄脆糖(brittle)、焦糖、太妃糖、甘草制剂、橡皮糖(jellies)、口香糖和胶,优选软胶。在本发明的甜食组合物的预期内晶体产品包含软糖料和乳脂、乳脂软糖(fudge)、牛轧糖、果汁软糖(marshmallow)、果仁糖、压制糖果例如片剂、蛋白杏仁酥糖和膏和小块糖果(panned candies)(抛光糖(dragee))。这些产品的组合也在甜食组合物的范围内。例如,巧克力涂覆的晶体或非晶体产品。
巧克力,在本发明预期内的一种重要的甜食组合物,包含甜巧克力、半甜巧克力、苦-甜(bitter-sweet)巧克力(其作为整体通常也被称为深色巧克力)、牛奶巧克力、酪乳(buttermilk)巧克力、脱脂乳(skim milk)巧克力和白巧克力。而且,任何一种填有坚果、水果、米粒和其他用于巧克力产品的填充物的上述巧克力也在本发明的范围内。巧克力还包括任何具有足以赋予巧克力味道、巧克力香味的性质的甜食产品和任何其他作为获得柔软蛋糕的巧克力类似物的材料。通过施用本发明的新型聚葡萄糖,所述巧克力、牛奶和/或深色巧克力为低热量的。进一步与赤藓醇组合,最终的巧克力为非生龋的且赤藓醇的冷却效果由于本发明的新型聚葡萄糖减少。
本发明还涉及包含本发明的聚葡萄糖和其他焙烤成分的焙烤产品。
其他焙烤成分对于本领域技术人员将为清楚的。它们可包括,例如:面粉、膨松剂(例如焙烤粉和/或酵母)、水和/或水混溶性液体(例如牛奶、醇等)、甜味剂(例如糖或人工甜味剂)、香料(例如合成的或天然的香料例如香草、焦糖和/或杏仁香料;水果汁例如桔、柚、梨、樱桃、悬钩子和/或黑醋栗汁;植物提取物例如番茄、胡萝卜、洋葱和/或大蒜提取物;香辛料(spice);药草等)和/或一种或多种天然或合成的着色剂。任选也可添加维生素(例如维生素A、D3、E、K1、C、B1、B2、B5、B6、B12和PP、叶酸和生物素)和矿物质(例如钠、钾、钙、磷、镁、氯、铁、锌、铜、锰、氟、铬、钼、硒和碘)。
用于焙烤产品的面粉可为任何来源(例如,玉米面粉、大豆面粉或小麦面粉)。然而,最优选的将为小麦面粉。将小麦面粉与其他面粉区别开并使其在焙烤工业中具有特别价值的是小麦面粉的蛋白,谷蛋白。在硬的、高蛋白小麦中,在其胚乳中具有较多谷蛋白并且淀粉细胞牢固地结合在一起。在软的、低蛋白小麦中该结合没有这么牢固。大多数蛋糕需要软的、低蛋白面粉。用于盘式面包生产的面粉将通常由高蛋白含量的硬小麦磨制,而软小麦可产生在一些国家最受欢迎的面包类型中最优的性质。理想的是,所述面粉将为非氯化的。
当然,其他焙烤成分的选择将取决于待生产的焙烤产品。事实上,本发明的聚葡萄糖可用于焙烤产品(例如蛋糕、饼干、曲奇饼干(cookie)、华夫饼干(waffle)、油炸圈饼(donuts)、松饼(muffin)、面包、脂肪填充物和焙烤奶油)的生产。
本发明的乳制品可选自牛奶、乳清、酸奶和基于它们的饮料;基于乳可可的饮料、发酵的甜品(例如新鲜干酪制品、可饮用的产品)、冰淇淋、中性乳甜品(例如布丁、果酱饼、vlas、乳脂沙司甜品(crèmedesserts)、搅打甜品)和加香料的酸奶制品(例如不含水果的水果酸奶)。用本发明的新型聚葡萄糖制备的冰淇淋具有较完全的质构(texture),含有较少水分,并表现出较多类似脂肪的乳脂状并且因其丰富的味道和质构而非常受欢迎。该质构好于使用市售聚葡萄糖的冰淇淋的质构。
饮料可为任何医用的或非医用的糖浆或任何可饮用的溶液(包括冰茶和水果汁、基于植物的汁、柠檬水、甜酒(cordial)和基于坚果的饮料)。它还包括饮料浓缩物和饮料粉。饮料浓缩物指为液体形式或基本为干混合物形式的浓缩物。液体浓缩物可为相对稠的、糖浆似液体的形式。基本干的混合物可为粉末或片剂的形式。通常制成饮料浓缩物以便在用碳酸化的或非碳酸化的水制作或稀释时提供可饮用的饮料组合物或最终的饮料。饮料粉适合用水(碳酸化的或非碳酸化的)或牛奶制作用于经口服用的最终饮料。
所述饮料还可包含其他糖类、蛋白质、肽、氨基酸、抗氧化剂、脂肪、维生素、痕量元素、电解质、强甜味剂、可食用酸、香料和/或其混合物。
所述其他糖类选自单糖、二糖、胶化淀粉、淀粉水解产物、糊精、纤维例如低热量纤维、多元醇及其混合物。
用作其他糖类的单糖包括丁糖、戊糖、己糖和己酮糖。
用作其他糖类的典型二糖包括蔗糖、麦芽糖、海藻糖(trehalulose)、蜜二糖、曲二糖、槐糖、昆布二糖、异麦芽糖、龙胆二糖、纤维二糖、甘露二糖、乳糖、明串珠菌二糖、麦芽酮糖(maltulose)、松二糖等。
用作其他糖类的淀粉水解产物通过控制的酸或酶促的淀粉水解来生产。它们可被细分成两种具体的种类,麦芽糖糊精和葡萄糖糖浆,并以它们的DE数(右旋糖当量)表征。事实上,DE数为存在于水解产物中的还原糖的百分比的量度,并用右旋糖以干重计算。麦芽糖糊精具有高至20的DE数,然而葡萄糖糖浆具有大于20的DE数。
用作其他糖类的糊精可按照糊精化方法制备。糊精化为存在或不存在酸时对干淀粉的热处理。
用作其他糖类的凝胶淀粉可包括乳化的淀粉例如淀粉正辛烯基琥珀酸酯。
所述低热量纤维可为阿拉伯半乳多糖、脱乙酰壳多糖、壳多糖、黄原胶、果胶、纤维素制品、魔芋(konjac)、阿拉伯树胶、大豆纤维、菊粉、改性淀粉、水解的瓜尔胶、瓜尔胶、β-葡聚糖、鹿角菜胶、刺槐豆胶、藻酸盐、聚二醇藻酸酯。
所述维生素可涉及维生素A、维生素C、维生素D、维生素E、维生素B12等。
可食用的酸可选自磷酸、柠檬酸、苹果酸、琥珀酸、己二酸、葡糖酸、酒石酸、富马酸及其混合物。优选该饮料的pH范围为约2至约6.5。这些酸可与用于粗聚葡萄糖提供步骤的那些相同或不同。
香料选自水果香料、植物香料及其混合物。优选的香料为可乐果香料、葡萄香料、樱桃香料、苹果香料和柑桔类香料例如桔香料、柠檬香料、酸橙香料、水果潘趣酒及其混合物。香料的量取决于选择的一种或多种香料(flavour or flavours)、需要的香料效果及使用的香料的形式。
如有需要,也可添加着色剂。任何被批准用于食物用途的水溶性的着色剂均可用于本发明。
有需要时,可添加防腐剂如山梨酸钾和苯甲酸钠。
出于质构和不透明性的目的也可将胶、乳化剂和油加入饮料。典型的成分包括羧甲基纤维素、单酸-和/或双酸-甘油酯、卵磷脂、果浆、棉籽油和植物油。它还可包含泡沫稳定剂例如丝兰或丝兰/皂树皮(quillaia)提取物。
本发明将在下文以一系列非限制性实施例的方式进行描述。
实施例
实施例1:
用色谱系统(来自Mitsubishi的ISMB单元)进行分离试验,所述色谱系统由串联的四个色谱柱组成,具有300升的柱床体积(BV)。该柱用强酸性阳离子(SAC)交换树脂(Mitsubishi UBK550以Na+-形式)填充,所述树脂由去离子水在60℃通过该柱15小时进行调节。使用的树脂为苯乙烯和二乙烯基苯(DVB)以8%交联制成的共聚物。用氢氧化钠水溶液(30%)将粗聚葡萄糖(1.71kg干物质,组成:1.5%包含酸的杂质、5.3%DP1、8.4%DP2、9.3%DP3、9.0%DP4、8.3%DP5、7.5%DP5-DP10、18.3%DP10-DP20、22.4%DP20-DP30、9.7%DP30-DP36和0.5%DP36+,以重量计)中和至pH接近7。
然后将加热的(55℃)中和的聚葡萄糖溶液(33.5°白利糖度(Brix))在柱的顶部注射。然后将该样品用去离子水在50℃的恒温以预定的0.15BV/hr的流速洗脱。定期收集样品,2种馏分得到分离:一种馏分包含低分子量馏分而第二种馏分包含具有需要的分子量分布型(见表1-精制的)的聚葡萄糖(0.8kg)。
具有需要的分子量分布型的聚葡萄糖(0.8kg)的GPC分析的结果如表1所示。
GPC分析用串联的两个柱:UltrahydrogelTM 500(Waters Corp.,美国)于环境温度和Rezex RSO Oligosaccharide(寡糖)(Phenomenex,美国)于80℃进行。
洗脱液为去矿化的、脱气的、无菌过滤的水,以0.2ml/min的流速应用。
检测器:Differential Refractometer(差示折射仪),且对于MW780,000-5,900,用Pullulan Standard Kit(支链淀粉标准试剂盒)P-82(Shodex,日本)进行分子量校准;对于MW 828-180,用CargillPolyol(Cargill多元醇)(例如Maltidex 163A6)进行分子量校准,用Electronical Integration(电子积分)进行定量。
表1:显示应用色谱步骤之前和之后的组合馏分的组成的GPC分析。
聚合度 | %DP+馏分 | 分子量 | 粗的 | 精制的 |
22800-11800 | 0.0 | 0.04 | ||
11800-5900 | 0.5 | 2.1 | ||
DP36-DP30 | 5900-4878 | 9.7 | 17.5 | |
DP30-DP20 | 4878-3258 | 22.4 | 33.5 | |
DP20-DP10 | DP20+:74.74 | 3258-1638 | 18.3 | 21.6 |
DP10-DP5 | DP10+:82.24 | 1638-828 | 7.5 | 7.5 |
DP5 | DP5+:90.74 | 828 | 8.3 | 8.5 |
DP4 | 666 | 9.0 | 6.7 | |
DP3 | 504 | 9.3 | 2.3 | |
DP2 | 342 | 8.4 | 0.2 | |
DP1 | 180 | 5.3 | 0.1 | |
杂质+酸 | 180* | 1.5 | 0.0 |
·杂质+残留酸
·DP:以葡糖酐单元表达的聚合度。
在色谱分离步骤之前对存在于未精制的聚葡萄糖中的柠檬酸的中和不仅去除了副产品(如5HMF、糠醛等)而且防止了它们的形成。
实施例1B:
不可消化的纤维含量的测定
‘精制的’聚葡萄糖的纤维含量通过使用大鼠肠酶的体外的消化系统测量。作为参考,包含异麦芽酮糖(isomaltulose)。
肠酶以大鼠肠丙酮粉购自Sigma。(Sigma编目#I1630,Sigma-Aldrich,St.Louis,MO,美国)。将粗粉按如下描述进一步纯化:
将10g大鼠小肠丙酮粉加入至200ml磷酸盐缓冲液(pH6.0,0.1M),并在4℃混合3h。将混合物在4℃以10000rpm离心10分钟(Sorval RC5CPLUS-Kendro Laboratory Products(Kendro实验室产品),Newtown,Connecticut,美国)。将上清液用滤纸真空过滤,然后用MWCO:25000膜(Spectra/Por Biotech Cellulose Ester(CE)DialysisMembranes(纤维素酯透析膜),Spectrum Laboratories,CA,美国)于4℃、磁力搅拌棒温和搅拌下在pH 6.0,0.1M,0.01%NaN3缓冲液中透析(10L,且每天换为新鲜缓冲液)3天。将所得溶液冻干。
活性检测用该纯化的小肠大鼠粉进行。使用与5.4ml 0.1M磷酸盐缓冲液培养的0.06g纯化的大鼠粉并加入0.6ml 0.1%异麦芽酮糖(最终0.01%异麦芽酮糖)来进行活性检测。这在37℃在玻璃试管中进行,并用小磁力搅拌棒搅拌。用Glucose-Test kit(葡萄糖测试试剂盒)(Reflectoquant 1.16720-Merck KgaA,Darmstadt,德国)测量右旋糖的释放。将60分钟后产生最少40ppm右旋糖的纯化的大鼠粉用于纤维测定。
将该聚葡萄糖与肠酶在以下条件下培养:
将0.15g纯化的大鼠肠粉溶解于5.4ml pH 6.0,0.05M磷酸盐缓冲液中。随后加入0.6ml 0.1%的样品。将反应混合物温和搅拌并在37℃培养。
几次时间间隔之后取1ml样品并立即用Glucose-Test(葡萄糖测试)(Reflectoquant 1.16720-Merck KgaA,Darmstadt,德国)测定存在于每个样品中的葡萄糖的量。
在2.3小时之后对于聚葡萄糖样品测量到93%不可消化的纤维,但是异麦芽酮糖被完全水解。
实施例2-巧克力:
实施例1的聚葡萄糖用于分别制备表2和3中的深色巧克力和牛奶巧克力。
表2:深色巧克力组成
% | |
麦芽糖醇 | 10.00 |
聚葡萄糖 | 19.00 |
赤藓醇 | 21.00 |
可可块 | 45.44 |
可可脂 | 4.00 |
三氯半乳蔗糖 | 0.013 |
香草 | 0.100 |
卵磷脂 | 0.450 |
总计 | 100.00 |
将这些成分在Z混合器中于45℃混合,以35rpm速率混合并以50-60rpm速率进行揉捏(conching)。
为生产深色巧克力,首先,将甜味剂(=麦芽糖醇、聚葡萄糖、赤藓醇和三氯半乳蔗糖(sucralose))放入Z混合器中。然后,加入部分可可块和部分可可脂。用3辊精制机进行精制。将精制后得到的粉末再次加入Z混合器1-3h。使Z混合器温度增加至70℃并且加入第二部分的可可块。14h后加入第二部分可可脂。使混合物的温度下降至50℃。在程序结束前一小时加入卵磷脂。
该巧克力为低热量的。
表3:牛奶巧克力组成
3-式共混 | |
麦芽糖醇 | 10.00 |
聚葡萄糖 | 18.50 |
赤藓醇 | 14.39 |
可可块 | 13.50 |
可可脂 | 16.00 |
乳脂 | 5.00 |
脱脂奶粉 | 22.00 |
三氯半乳蔗糖 | 0.020 |
香草 | 0.020 |
卵磷脂 | 0.570 |
总计 | 100.00 |
脂肪含量 | 29.1 |
热量值 | 397.5 |
表3显示了包含赤藓醇、麦芽糖醇和本发明的聚葡萄糖的牛奶巧克力产品(3-式共混(3-way blend))。
该牛奶巧克力为低热量的。最终的巧克力为非生龋的且赤藓醇的冷却效果由本发明的新型聚葡萄糖降低。
实施例3-冰淇淋
表4中,给出了三种包含实施例1的聚葡萄糖的冰淇淋组合物。
奶油冰淇淋可通过应用实施例1的聚葡萄糖来制备。
表4
将干成分(除了脂肪)一起混合。全部加热至40-45℃的温度,然后在水中混合。
加入脂肪并开始加热,在85℃消毒5分钟,然后于80-85℃在两步均化器中在150/50巴均化。使产物通过直列管式换热器(水冷却的)达到25-30℃并且将其收集至槽中。在持续搅拌时快速冷却至4℃并在4℃至少保持4小时(熟化)。
将冰淇淋在连续冰箱中挤压,出口温度为-6至-6.5℃。
将1L的箱子填充并置于-35℃冰箱中16小时,并且在-18℃进行储存。
与含有市售的聚葡萄糖的冰淇淋相比,该冰淇淋具有令人愉快的类脂肪的奶油状且不是多水的。
实施例4-饮料
碳酸可乐饮料
具有4%果糖、3%实施例1的聚葡萄糖和高甜度甜味剂(highintense sweetener)的中热量可乐。
表5:配方
聚葡萄糖 | 188.1g |
阿斯巴甜(aspartame) | 466.2mg |
乙酰舒泛K | 239.4mg |
无水咖啡因(ZX0116) | 0.57g |
果糖 | 240g |
苯甲酸钠10%(w/v) | 9.5g |
可乐乳液AK 0610(Duckworth) | 12.5g |
正磷酸85% | 6.8g |
加SpaTM水以达到 | 1升 |
程序:
将适量SpaTM水加入烧杯中,加入必要量的聚葡萄糖并搅拌直到溶解。将全部混合物加热至最高50℃。然后,将其他成分加入直到溶解并加热至最高50℃。
然后,将35ml此种基本糖浆加入瓶中并用碳酸水稀释以得到210ml体积。
评估:
包含本发明的聚葡萄糖的样品具有约7°白利糖度的比重和约2.7的pH。
与含有替代的等量的常规聚葡萄糖(Litesse)的混合物比较时,两者都具有好的可乐气味,但含有本发明的聚葡萄糖的这种与含有常规Litesse聚葡萄糖的可乐相比不那么强烈。
颜色不是可乐配方中的问题。
味道:
含有本发明的聚葡萄糖的可乐产品比其他常规聚葡萄糖可乐饮料具有更好的可乐味道。本发明的产品被认为具有较少的人工味道并没有粉末味道。
含水果汁的饮料
含7%实施例1的聚葡萄糖和高甜度甜味剂的低热量桔子软饮料
表6:配方
程序:
适量SpaTM水加入烧杯中,加入必要量的聚葡萄糖并搅拌直到溶解。将全部混合物加热至最高50℃。然后,加入其他成分直到溶解并加热至最高50℃。
气味:
所有样品都具有好的桔子气味-没有真正的不同
味道:
好的桔子感觉,有点人工余味
具有4%实施例1的聚葡萄糖、3%赤藓醇和高甜度甜味剂的中热量的桔子软饮料
表7:配方
所有样品具有约7.6°白利糖度的干物质和约3.1的pH。
程序:
适量SpaTM水加入烧杯中,加入必要量的聚葡萄糖并搅拌直到溶解。将全体混合物加热至最高50℃。然后,加入其他成分直到溶解并加热至最高50℃。
味道:
好的桔子感觉,几乎没有人工余味
实施例5:软胶
不含聚葡萄糖的软胶配方(参考材料)和含有实施例1的聚葡萄糖的软胶配方
表8:配方
将部分A溶解于热水(温度80-90℃)中。使其保持于该温度直到获得需要的白利糖度。
将部分B溶解于温度为90℃的热水中。
将部分A和B(比率A∶B:83/17)混合并向共混物中加入柠檬酸。在78-84℃的温度出现沉淀。
该方法对于用实施例1的聚葡萄糖制备的软胶得到满意的结果。
实施例6:
体外测定实施例1的聚葡萄糖的生龋性。
实验的
使用的方法为体外生龋性试验。该试验中在限定条件下对糖类通过口腔细菌变异链球菌(Streptococcus mutans)的‘体外’可发酵性进行研究。该试验如下进行:在由简单氮源组成且试验物为唯一碳源,用生理缓冲液缓冲的培养基中,记录有机酸随时间的产生。
a.培养基组成部分
糖类:0.85M储备溶液。试验体积中的终浓度为170mM。
氮源:6.7%d.s.酵母氮基(Yeast Nitrogen Base)(YNB,来自Difco)。试验中的终浓度为0.67%d.s.。
缓冲液:将1.25M MES(吗啉代乙磺酸)悬液用浓NH4OH调节至pH=7.2(pH调节过程中MES被溶解)。试验中的终浓度为0.25M。
将溶液过滤(0.22μ)除菌。
每支无菌的‘体外’试管(15x150mm,金属塞子)包含如下成分(对于10ml的试验):
2ml糖类储备溶液(0.85M)
2ml MES-缓冲液
1ml YNB-溶液
4.5ml无菌蒸馏水
0.5ml接种物
测试低生龋底物时通常使用5ml试验,因为高接种物密度是这些底物所需的;对于生龋底物(如蔗糖、右旋糖)该试验以10ml进行。
b.接种物制备
将变异链球菌-TCV264(ATCC25175)从TBA基(胰蛋白血琼脂基)斜面转移至1L烧瓶中的TSB(胰蛋白酶大豆肉汤)-MES缓冲液(3%TSB-0.06M),pH7.2,以制备储存培养物,并在37℃生长。100冲程/分钟震荡16小时。通过离心(3000g,10分钟)浓缩细菌。用生理缓冲液(0.04%NaCl,0.3KH2PO4,0.7%Na2HPO4·2H2O,+0.5%吐温80)洗涤细胞并再次离心。
将最终的沉淀用最小体积(25ml)的相同缓冲液重悬,以含有约2-5×10e10细胞/ml。
将该储存培养物转移至无菌REVCO-管瓶(1ml/管瓶),立即于液氮中冷冻并于-70℃储存。
将含有冷冻的变异链球菌细胞的管瓶用于接种含500mlTSB-MES缓冲液的无菌0.5L烧瓶,在水浴中轻微搅动以使细胞分散。该培养物在如上所述的相同条件下生长5-7小时(pH=6.3-6.4且O.D.660=0.8-0.9)。
然后收获细胞并重悬于10ml生理缓冲液(=50×浓缩的)中。在含有胆汁七叶苷琼脂(Bile Esculin Agar)的斜面上进行对照平板接种以检查该细胞悬液的纯度和浓度。
由于操作的原因和难以对链球菌进行活细胞计数,因此通过在作为底物的右旋糖上的接种物的培养几次估计细胞密度,使用三种不同量的细胞,并观测酸产生速率。作为该试验的接种物,使用1.0ml上述得到的悬液以接种该体外试验的试管。
所有操作均在无菌环境中进行。
c.体外试验条件和取样
对接种的试管在37℃培养,不用震荡。即将取样前使试管在Vortex(涡旋)上搅动。以适当的时间间隔,取出无菌样品(1.2ml),在3000g离心5′并将上清液用0.45μ过滤器(未经灭菌的)过滤。测定pH。转移0.75ml样品。
根据研究的糖类的类型,选择不同的接种物浓度和不同的取样时间间隔。
对于多元醇和可选择的甜味剂,在16至40小时间隔后监测酸的释放,在试管中使用约5×10e9细胞/ml接种物。
对于葡萄糖、果糖、蔗糖和其他可发酵的糖类,较快产生酸需要1至24小时的间隔和试管中低至1/10的接种物。
结果的分析和计算
通过HPLC用Sodex KC811-柱以H+形式在65℃测定有机酸。并用0.01%H2SO4以0.8ml/min洗脱,注射体积为25μ;用UV在210nm检测。
记录乳酸、甲酸和乙酸峰的面积并用丁酸作为内标进行校准。HPLC结果以微摩尔酸/ml或mM表达。
使用的接种物浓度为3.5×108细胞/ml。测量有机酸的释放和ADR(某一培养时间之后总酸度/hr,mM/hr,总酸度被定义为乳酸、甲酸和乙酸的总和)。
结果在下表中给出:
表9:
体外生龋数据表明实施例1的聚葡萄糖基本为非生龋的且比市售聚葡萄糖更少生龋。
Claims (12)
1.制备聚葡萄糖的方法,所述聚葡萄糖包含至少75%重量的具有5或更大的聚合度的糖分子且其不可消化的纤维含量为至少80%重量,所述方法包括如下步骤:
a)提供粗聚葡萄糖,
b)将pH调节至7,和
c)色谱分离为至少两种级分,其中一种级分富含具有1至4的聚合度的糖分子,而另一种级分富含所述聚葡萄糖。
2.权利要求1的方法,其特征在于所述粗聚葡萄糖由糖和任选的糖醇在酸存在时经缩聚提供。
3.权利要求1或2的方法,其特征在于所述粗聚葡萄糖仍含有用于聚合反应的残留酸。
4.权利要求1或2的方法,其特征在于所述糖为葡萄糖、右旋糖、麦芽糖或淀粉水解产物。
5.权利要求1或2的方法,其特征在于所述糖醇是以下一种或多种:丙三醇、赤藓醇、苏糖醇、戊糖醇以及己糖醇。
6.权利要求5的方法,其特征在于所述戊糖醇是木糖醇,所述己糖醇是山梨醇、甘露醇或半乳糖醇。
7.权利要求1或2的方法,其特征在于所述糖醇是一种或多种己糖醇。
8.权利要求7的方法,其特征在于所述糖醇是一种或多种山梨醇。
9.权利要求1或2的方法,其特征在于所述酸为可食用的酸,选自磷酸、柠檬酸、苹果酸、琥珀酸、己二酸、葡糖酸、酒石酸、富马酸及其混合物。
10.权利要求1或2的方法,其特征在于步骤b)中,通过加入液体碱性化合物使粗聚葡萄糖的pH增加。
11.权利要求10的方法,其特征在于,所述液体碱性化合物为溶于水的氢氧化钠或其他合适的碱化化合物。
12.权利要求1或2的方法,其特征在于所述步骤c)包括用强酸性阳离子交换树脂的色谱分离。
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DE102012004307A1 (de) * | 2012-03-01 | 2013-09-05 | Merz Pharma Gmbh & Co. Kgaa | Instant-Zubereitungen mit Polydextrose, Herstellung und Verwendung |
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CN104304401A (zh) * | 2014-11-24 | 2015-01-28 | 泉州亲亲食品有限公司 | 一种添加聚葡萄糖的华夫饼及其制备方法 |
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US10258647B2 (en) | 2015-09-01 | 2019-04-16 | Particle Dynamics International, Llc | Iron-polysaccharide complexes and methods for the preparation thereof |
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JP2019510036A (ja) | 2016-03-31 | 2019-04-11 | ゴジョ・インダストリーズ・インコーポレイテッド | プロバイオティクス/プレバイオティクス有効成分を含む清浄剤組成物 |
AU2017365019A1 (en) | 2016-11-23 | 2019-07-11 | Gojo Industries, Inc. | Sanitizer composition with probiotic/prebiotic active ingredient |
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