CN1697607A - 类胡萝卜素制剂 - Google Patents
类胡萝卜素制剂 Download PDFInfo
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- CN1697607A CN1697607A CNA028273958A CN02827395A CN1697607A CN 1697607 A CN1697607 A CN 1697607A CN A028273958 A CNA028273958 A CN A028273958A CN 02827395 A CN02827395 A CN 02827395A CN 1697607 A CN1697607 A CN 1697607A
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- lycopene
- protein
- modification
- colloid
- food
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- Jellies, Jams, And Syrups (AREA)
Abstract
本发明公开了使用含有两亲性蛋白质聚合物的非水溶性薄膜包衣的番茄红素用于将脂肪和/或油类含量高于5％的食品、药品和化妆品着以红色的应用。本发明进一步公开了制备稳定的番茄红素制剂的方法，它包括：(a)处理分离的蛋白质以形成分子形式的蛋白质；(b)将番茄红素分散于含有分子形式的分离蛋白质的水溶液中；(c)研磨所述分散体以形成大小为1－10μm的番茄红素颗粒，从而形成含有微细颗粒的均质混合物；以及任选地(d)干燥该均质混合物。
Description
发明领域
本发明属于番茄红素制剂领域，涉及番茄红素的制备方法及其作为添加剂特别是作为着色剂的应用，这种着色剂保留了番茄红素的独特颜色。
发明背景
番茄红素属于类胡萝卜素一类的天然物质，富含于各种水果和蔬菜中。自然界所发现的这种化合物的反式/顺式比例为90∶10，不溶于水，在油类或脂肪中的溶解性相当有限。研究表明，经常食用番茄红素与减少慢性疾病例如心脏和循环疾病有关。另外，它还有助于预防几种类型的癌症。其保护功能归因于这样一个事实，那就是番茄红素可作为有效的抗氧化剂。其独特的深红色(intense red color)使得它可用作天然的食品着色剂。番茄红素既可以合成得到(EP382,067)，也可以由含番茄红素浓度比较高的番茄提取得到(WO97/48,287)。
然而，番茄红素作为食品添加剂的应用存在几个问题。其溶解性成问题，它不溶于水，仅仅微溶于油类和脂肪。另外，它容易被氧化。除这些以外，番茄红素只有在分散于水中并且颗粒大小为1-10μm，优选为1-3μm时才具有独特的红色。更大尺寸的颗粒作为着色剂的效果有所降低。此外，一旦与油发生接触，番茄红素颗粒会发生溶解同时赋予一种橙色至黄色的颜色。
这样一来使得番茄红素只能用于特殊的制剂中，在这些制剂中番茄红素受某些添加剂保护以防止氧化和/或番茄红素以细分散颗粒的形式出现。WO 91/06292和WO 94/19411中描述了一种研磨β-胡萝卜素的方法，该方法可以获得大小为2-10μm左右的颗粒。在EP 832569和WO 98/16204中报道了一种含有番茄红素的干燥粉末，其可用作水分散性粉末。US 6,235,315中公开了一种稳定的粉状番茄红素制剂，其含有结晶度大于20％的番茄红素。通过加入保护性胶体、稳定剂和可塑剂可以增加粉状制剂的稳定性。US 2002/0128325公开了一种制备稳定的类胡萝卜素粉末的方法，其中将类胡萝卜素分散于含有保护性胶体和乳糖的溶液中，以及这种粉末在药品、食品和化妆品中的应用。
发明概述
本发明是基于用一种薄膜将固状结晶微粉化的番茄红素颗粒包衣的方法，该薄膜含有水溶性的两亲性生物共聚物例如蛋白质或蛋白质与水胶体的混合物，一旦这种薄膜在番茄红素周围沉淀下来就形成了一种非水溶性网状薄膜。将番茄红素置于含油脂的水相中后，这样的薄膜的形成可以产生受保护的番茄红素，防止固体形式或分子形式的番茄红素迁移入油脂/油类/脂肪中。这样一来，这种包衣的番茄红素使得可以在脂质相中使用番茄红素同时仍然保持其典型的红色，如果番茄红素迁移入油脂/油类/脂肪相中将得到黄色分子。因此，这样的包衣番茄红素可用作脂质含量高于5％的食品、药品或化妆品的添加剂或着色剂。
因此，本发明的目的在于用含有两亲性蛋白质聚合物的非水溶性薄膜包衣的番茄红素用于将脂质含量高于5％的食品、药品或者化妆品着以红色的应用。非水溶性薄膜还可进一步含有胶体。包衣番茄红素可以是任意来源的番茄红素，例如合成番茄红素、番茄浆或者从生物质(biomass)，优选番茄浆中提取的番茄红素。
本发明的另一目的是制备稳定的番茄红素制剂的方法，它包括：
(a)处理分离的蛋白质以形成分子形式的蛋白质；
(b)将番茄红素分散于含有分子形式的分离蛋白质的水溶液中；
(c)研磨所述的分散体以形成大小为1-10μm的番茄红素颗粒，从而形成含有微细颗粒的均质混合物；以及任选地
(d)干燥该均质混合物。
该方法还可以包括将所述番茄红素颗粒与至少一种胶体在水中混合接着再干燥的步骤。任选地，可以单独地将番茄红素研磨后再加入至分离的蛋白质的水溶液中。
所用的番茄红素可以是任意来源的番茄红素，例如合成的、天然提取到的或者含有生物质的粗番茄红素。该制剂还可以含有抗氧化剂和/或乳化剂。所有加入番茄红素中形成制剂的添加剂都是食品级(food-grade)的。
本发明的另一目的是含有由上述方法得到的干燥粉末的番茄红素。这样的干燥粉末通常含有番茄红素的量为1％-15％(w/w)，优选4％-8％。
本发明的再一目的是使用这种干燥均质番茄红素制剂将油类或脂肪含量至少为5％的食品、化妆品或药品着以天然红色的方法。
本发明的详细描述
下面的描述仅仅是对本发明实施方案的示例。下面的描述不能被解释为限制性描述，而应该理解为技术人员可以对这些方法进行各种显而易见的改变。
在通篇说明书中，百分比是指重量比重量，除非另有特别的不同的注明。术语“脂质”包括油类和脂肪。
正如所提及到的那样，本发明目的在于用含有两亲性蛋白质聚合物的非水溶性薄膜包衣的番茄红素将脂质含量高于5％的食品、药品或者化妆品着以红色的应用。本发明另一目的在于配制番茄红素的方法，这样的方法使得它可用于脂质含量高于5％的食品、药品或者化妆品中而同时仍然保持其红色。番茄红素一旦与具有这样的油类或脂肪含量的食品、药品或者化妆品发生接触，它就很容易溶解于脂质相中。溶解的结果就是失去其独特的红色。因此，为了防止这种迁移，并且保证番茄红素可用作那些具有高油类或脂肪含量的基质的添加剂同时保持其独特的红色，本发明公开了将番茄红素包衣的方法。根据本发明，番茄红素是用透明薄膜包衣的，这样可以阻止番茄红素迁移入油相或脂肪相中。该透明薄膜由两亲性蛋白质组成。另外一种选择是向蛋白质包衣的番茄红素中加入胶体。可根据本发明包衣的番茄红素可以为任意形式的番茄红素，非限制性实例有合成番茄红素、由其天然来源提取的番茄红素，例如番茄或者甚至是一种含有番茄红素的天然生物质。本发明所用的两亲性蛋白质是在其链上具有亲脂性氨基酸的蛋白质。可以赋予所需的亲脂性的氨基酸实例有亮氨酸、异亮氨酸、苯丙氨酸以及缬氨酸。另外还可以使用这样的蛋白质，它由在其链上低含量的胱氨酸和半胱氨酸组成，并且只有在压力或温度的极限条件下它才可能发生交联。这样的蛋白质具有表面活性，一旦与任意形式的番茄红素发生接触，它就会与番茄红素纤维发生相互作用并吸附在其表面，从而形成将番茄红素纤维包衣的蛋白质薄层。这种蛋白质的非限制性实例有疏水性的改性的大豆蛋白、乳清蛋白质分离物、卵清蛋白质、溶菌酶、改性豌豆蛋白以及明胶或其混合物。可通过水解蛋白质、化学反应或酶将蛋白质改性。天然的三维立体结构的蛋白质不能用作包衣膜。更适宜的是应该通过下述步骤先将蛋白质转化为分子形式：将蛋白质分散于水中，调节pH为9-10，加热该分散体，冷却再冻干。
某些胶体可能因为疏水性或者电荷相互作用而被蛋白质吸引形成蛋白质-胶体配合物。因此，除了用两亲性蛋白质包衣番茄红素之外，根据本发明的番茄红素还可以用蛋白质-胶体薄膜包衣，该蛋白质-胶体薄膜是由于两亲性蛋白质与胶体发生相互作用而形成的含有蛋白质和胶体的包衣膜。这种膜如果被有效地吸附得很牢固，它就可以耐住水的稀释并且阻止番茄红素迁移入油相和脂肪相中。这种胶体的非限制性实例有蛋白质多糖水胶体或保护性胶体，其中所述蛋白质多糖水胶体选自阿拉伯树胶、黄原胶、酰胺化了的淀粉、酰胺化了的果胶；所述保护性胶体选自食品级的多糖、多糖，或者选自果胶、海藻酸盐、黄原胶、黄蓍胶或其改性结构的树胶，改性淀粉，改性壳聚糖，麦芽糖糊精，改性甲基纤维素，半乳甘露聚糖或其混合物。
根据本发明，番茄红素粉末是通过这样制成制剂的：将番茄红素分散于含有分子形式的分离蛋白质的水溶液中，均质研磨该分散体得到颗粒大小为1-10μm、优选1-5μm、最优选1-3μm的番茄红素颗粒，这种番茄红素粉末既可以是干燥的生物质、也可以是结晶状的或者湿的生物质。应该理解研磨是保证番茄红素被蛋白质包衣的先决条件。这样的研磨确保了将全部番茄红素纤维包衣到蛋白质薄膜中。所得到的溶液含有包衣番茄红素，它可用于着色和/或食品、药品或者化妆品中的添加剂。作为替代方式，可以干燥番茄红素得到粉末，其中番茄红素含量为1％-15％(w/w)，优选2％-10％，最优选4％-8％。
正如所提及到的那样，将番茄红素包衣的蛋白质薄膜还可以借助于可能的疏水或电荷作用与胶体相互作用而形成含有与胶体结合的蛋白质的包衣膜。应该注意，无论是蛋白质包衣膜还是蛋白质/胶体包衣膜均还可以进一步含有在研磨阶段加入的抗氧化剂和/或乳化剂。这种抗氧化剂和/或乳化剂是在加入至少一种胶体时加入的。抗氧化剂的非限制性实例有抗坏血酸、柠檬酸、生育酚或者棕榈酸抗坏血酸酯(ascorbel palmitate)。将抗坏血酸和柠檬酸(重量比例为1∶1)的混合物加入至含有番茄红素/蛋白质干燥粉末和胶体的水溶液的混和物中。乳化剂的非限制性实例有吐温、聚甘油酯、糖酯、卵磷脂(lecitins)、蓖麻油以及乙氧基化的蓖麻油。
根据本发明的一个具体实施方案，包衣番茄红素被用作食品、药品和化妆品的着色剂。因此，该包衣的番茄红素制剂被加入至食品、药品和化妆品中以赋予它们红色。将所述番茄红素制剂在制备食品、药品和化妆品的过程中加入至其中。在所述制备方法中加入番茄红素制剂的时机可以不同，可由技术人员把握。
使产品呈现出所需红色的番茄红素制剂的有效用量可以不同。所加入番茄红素制剂的用量是基于番茄红素计算的，其中番茄红素的用量为10-200ppm。
现在通过下面的非限制性实施例对本发明进行描述，其中应该强调的是，计算番茄浆与大豆的重量比是基于所述产物组合物中含有10-200ppm番茄红素而进行的。番茄浆就是从番茄中除去大部分的水溶性部分后得到的生物质。番茄浆可以不经处理直接使用或者在使用之前先干燥。
实施例
实施例1：给结晶番茄红素包衣的方法
将100g分离的大豆蛋白SUPROEX34K(Protein TechnologiesInternational Belgium)溶解于1000g水中(40-50℃，30分钟)。向溶液中加入50g纯的结晶番茄红素(Lyc-O-Mato70％)。充分混合得到均质混合物，将其在球磨机中研磨得到颗粒直径为1-3μm的番茄红素。研磨后的番茄红素与650g改性淀粉(Mira cup，Staley，USA)以及1000g水进行混合(混合物的TDS大约为30％)。立刻将混合物喷雾干燥，得到冷的耐水分散性耐油的粉末，其番茄红素含量接近6％(Lyc-O-Mato6％OR)。
实施例2：将结晶番茄红素包衣的工业化方法
溶解2.5kg大豆分离蛋白EX 33K(PTI生产)得到6％的蛋白质水溶液(41.7kg溶液)，将pH调节在9-10的范围内，在80℃下煮溶液1小时。以占总固体(pH保持在9-10)的1％(各0.04kg)的用量加入抗氧化剂棕榈酸抗坏血酸酯和生育酚。将1kgP番茄红素(1.54kg 65％番茄红素)与蛋白质溶液混合均匀{其中所得到的43kg溶液可用作饮用混合物，它含有4.12kg总固体和2.32％番茄红素}。然后将该均匀混和的蛋白质-番茄红素溶液进行研磨，之后加入7.7kgMira cap(改性淀粉)并使其均匀。干燥前的TDS为23.3％番茄红素在干燥终产物中的浓度为8.04％，湿度为5％。各成分的量汇总于下表。
| Lyc-O-Mato 70％ | 1kg纯(1.54kg未经处理) | |
| 蛋白EX 33K | 2.5kg | |
| 棕榈酸抗坏血酸酯 | 0.04kg | |
| α-生育酚 | 0.04kg | |
| Mira cap | 7.7kg | |
| 总固体 | 11.82kg | |
| 干燥产物中的番茄红素 | 8.46％ | |
| 湿度为5％的干燥粉末中的番茄红素 | 8.04％ |
应用：含有0.8g Lyc-o-mato8％ OR的1000g植物蛋白质(脂肪含量为16％)的混合物。包装于聚乙烯套中在90℃下煮30分钟。煮后颜色为粉红色，无橙色色调。
实施例3
将0.1g分离的大豆蛋白EX-34K分散于99g水中。使用0.5M NaOH调节悬浮液的pH至9.2。在70℃下加热分散体30min。冷却至室温并冻干干燥。将0.1g冻干粉末(水溶性蛋白质)溶解于100g水中。加入10g番茄浆(Lycored)。使用″Silverson″分散机(1000rpm)将浆料悬浮液匀浆。通过喷雾干燥法干燥含有蛋白质的干燥浆。
应用：将干燥的粉末(10.1g)加入1270g大豆物料(soy mass)(″Tivall″)中，均匀化，真空包装于专用袋中，在水中加热(90℃，15min.)然后贮存。大豆物料(soy mass)保持粉红色。
实施例4
将0.1g分离的大豆蛋白EX-34K分散于99g水中。使用0.5M NaOH调节悬浮液pH至9.2。在70℃下加热分散体30min。冷却至室温。向所制得的溶液(水溶性的蛋白质溶液)中加入10g番茄浆(Lycored)。仿照实施例3继续后面的步骤。
实施例5
将0.05g分离的大豆蛋白EX-34K分散于99g水中。使用0.5MNaOH调节悬浮液pH至10.2。在70℃下加热分散体30min，然后冷却至室温。冻干干燥。将0.1g冻干粉末溶解于100g水中。加入10g番茄浆(Lycored)。将悬浮液匀化。通过喷雾干燥法干燥。
应用：将干燥粉末加入1270g大豆物料(soy mass)(″Tivall″)中，匀浆，真空包装于专用袋中，在水中加热(90℃，15min.)然后贮存。大豆物料(soy mass)保持粉红色。
实施例6
将0.2g分离的大豆蛋白590分散于99g水中。按照需要使用0.5M NaOH调节悬浮液pH至9.2。在70℃下加热分散体30min。冷却至室温并冻干干燥。将0.2g冻干粉末溶解于100g水中。加入11g番茄浆(Lycored)，将浆状悬浮液匀浆(Silverson装置)。通过喷雾干燥法干燥含有蛋白质的浆液。
应用：将干燥粉末(11.2g)加入至1270g大豆(soy mass)(″Tivall″)中，匀浆，真空包装于专用袋中，在水中加热(90℃，15min.)然后贮存。大豆物料(soy mass)保持粉红色。
实施例7
将0.5g分离的大豆蛋白590分散于99g水中。使用0.5M NaOH调节悬浮液pH至9.4。在70℃下加热分散体30min。冷却至室温。向所制得的水溶性蛋白质溶液中加入10g番茄浆(Lycored)。将分散体匀浆(Silverson装置)并通过喷雾干燥法干燥。
应用：将干燥粉末(10.5g)加入至1270g大豆物料(soy mass)(″Tivall″)中，匀浆，真空包装于专用袋中，在水中加热(90℃，15min.)，然后贮存。
尽管结合具体实施方式对本发明进行了描述，但是很明显，本领域技术人员根据前面的描述进行诸多改变和替换是显而易见的。因此，本发明的目的是包括那些落入所附的权利要求书的精神范围之内的所有替代方式以及变型。
Claims (22)
1.用含有两亲性蛋白质聚合物的非水溶性薄膜包衣的番茄红素的应用，它用于将脂肪和/或油类含量高于5％的食品、药品或化妆品着以红色。
2.根据权利要求1的应用，其中所述番茄红素选自合成番茄红素、番茄浆或者从生物质，优选从番茄浆提取出来的番茄红素。
3.根据权利要求1的应用，其中所述两亲性蛋白质选自对疏水性进行了改性的大豆蛋白、乳清蛋白质分离物、卵清蛋白质、溶菌酶、改性的豌豆蛋白、明胶或其混合物。
4.根据权利要求1的应用，其中所述非水溶性薄膜还含有胶体。
5.根据权利要求4的应用，其中所述胶体选自蛋白质多糖水胶体或保护性胶体，其中所述蛋白质多糖水胶体选自阿拉伯树胶、黄原胶、酰胺化了的淀粉、酰胺化了的果胶；所述保护性胶体选自食品级的多糖，或者选自果胶、海藻酸盐、黄原胶、黄蓍胶或其改性的结构，改性淀粉，改性壳聚糖，麦芽糖糊精，改性甲基纤维素，半乳甘露聚糖或其混合物。
6.用于制备稳定的番茄红素制剂的方法，它包括：
(a)处理分离的蛋白质以形成分子形式的蛋白质；
(b)将番茄红素分散于含有分子形式的分离蛋白质的水溶液中；
(c)研磨所述分散体以形成大小为1-10μm的番茄红素颗粒，从而形成含有微细颗粒的均质混合物；以及任选地
(d)干燥该均质混合物。
7.根据权利要求6的方法，还包括将所述番茄红素颗粒与至少一种胶体在水中混合接着再干燥的步骤。
8.根据权利要求6或7的方法，其中所述番茄红素选自合成番茄红素、番茄浆或者从生物质优选从番茄浆提取出来的番茄红素。
9.根据权利要求6的方法，其中所述分离的蛋白质是两亲性的，并且选自对疏水性进行了改性的大豆蛋白、乳清蛋白质分离物、卵清蛋白质、溶菌酶、改性的豌豆蛋白、明胶或其混合物。
10.根据权利要求7的方法，其中所述胶体是蛋白质多糖水胶体或保护性胶体，其中所述蛋白质多糖水胶体选自阿拉伯树胶、黄原胶、酰胺化了的淀粉、酰胺化了的果胶；所述保护性胶体选自食品级的多糖，或者选自果胶、海藻酸盐、黄原胶、黄蓍胶或其改性的结构，改性淀粉，改性壳聚糖，麦芽糖糊精，改性甲基纤维素，半乳甘露聚糖或其混合物。
11.根据权利要求6或7的方法，其中所述番茄红素制剂还含有抗氧化剂和/或乳化剂。
12.根据权利要求11的方法，其中所述抗氧化剂选自抗坏血酸、柠檬酸、生育酚或者其混和物。
13.含有由权利要求6的方法得到的干燥粉末的番茄红素。
14.含有由权利要求7的方法得到的干燥粉末的番茄红素。
15.含有如权利要求13或14所述的干燥粉末的番茄红素，其番茄红素含量为1％-15％(w/w)，优选4％-8％。
16.将油或脂肪含量高于5％的食品、药品和化妆品着以天然红色的方法，它包括加入含有权利要求13的粉末的番茄红素。
17.将油或脂肪含量高于5％的食品、药品和化妆品着以天然红色的方法，它包括加入含有权利要求14的粉末的番茄红素。
18.用含有至少一种聚合物的非水溶性薄膜包衣的番茄红素，它用于将油类或脂肪含量高于5％的食品、药品和化妆品着以红色。
19.根据权利要求18的包衣的番茄红素，其中所述番茄红素选自合成番茄红素、番茄浆或者从生物质，优选从番茄浆提取出来的番茄红素。
20.根据权利要求18的包衣番茄红素，其中所述两亲性蛋白质选自对疏水性进行了改性的大豆蛋白、乳清蛋白质分离物、牛血清清蛋白、酪蛋白、乳球蛋白、卵清蛋白质、溶菌酶、改性的豌豆蛋白、明胶或其混合物。
21.根据权利要求18的包衣的番茄红素，其中所述非水溶性薄膜还含有胶体。
22.根据权利要求21的应用，其中所述胶体选自蛋白质多糖水胶体或保护性胶体，其中所述蛋白质多糖水胶体选自阿拉伯树胶、黄原胶、酰胺化了的淀粉、酰胺化了的果胶；所述保护性胶体选自食品级的多糖，或者选自果胶、海藻酸盐、黄原胶、黄蓍胶或其改性的结构，改性淀粉，改性壳聚糖，麦芽糖糊精，改性甲基纤维素，半乳甘露聚糖或其混合物。
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| CN104883906A (zh) * | 2012-08-26 | 2015-09-02 | 利库德有限公司 | 色彩受控制的β-胡萝卜素制剂 |
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| CA2591772C (en) | 2004-12-22 | 2013-05-14 | Colarome Inc. | Natural water-insoluble encapsulation compositions and processes for preparing same |
| CA2767935A1 (en) * | 2009-07-31 | 2011-02-03 | Ecology Coatings, Inc. | Coated substrates and methods of preparing the same |
| US8273560B2 (en) * | 2010-07-30 | 2012-09-25 | Ecology Coatings, Inc. | Coated substrates and methods of preparing the same |
| US20130251855A1 (en) * | 2012-03-21 | 2013-09-26 | Pepsico, Inc. | Aqueous product comprising oil-containing microcapsules and method for the manufacture thereof |
| CN104274428B (zh) * | 2013-07-09 | 2016-04-13 | 浙江新维普添加剂有限公司 | 油分散性类胡萝卜素制剂的制备方法 |
| DK3102185T3 (da) * | 2014-02-03 | 2021-10-04 | Apurano Pharmaceuticals Gmbh | Nanosuspension af naturlige materialer og fremgangsmåde til fremstilling deraf |
| WO2019099338A1 (en) * | 2017-11-15 | 2019-05-23 | Wisconsin Alumni Research Foundation | Insoluble and dispersible protein and dye-containing particles for use as colorants |
| CN112708956B (zh) * | 2021-01-08 | 2022-11-18 | 安徽大学 | 一种基于静电纺丝的负载番茄红素的复合纳米纤维、制备方法及应用 |
| CN116211723B (zh) * | 2023-04-07 | 2024-05-03 | 江西广恩和药业股份有限公司 | 一种滋养润肤保湿乳及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104883906A (zh) * | 2012-08-26 | 2015-09-02 | 利库德有限公司 | 色彩受控制的β-胡萝卜素制剂 |
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| US10206965B2 (en) | 2019-02-19 |
| CN100456961C (zh) | 2009-02-04 |
| EP1455598B1 (en) | 2014-11-12 |
| EP1455598A1 (en) | 2004-09-15 |
| CA2468303C (en) | 2013-07-23 |
| US20050175561A1 (en) | 2005-08-11 |
| AU2002356404B2 (en) | 2008-12-11 |
| IL146737A0 (en) | 2002-07-25 |
| AU2009200943A1 (en) | 2009-04-02 |
| CA2468303A1 (en) | 2003-06-05 |
| WO2003045167A1 (en) | 2003-06-05 |
| US20080287551A1 (en) | 2008-11-20 |
| IL146737A (en) | 2010-02-17 |
| ES2526802T3 (es) | 2015-01-15 |
| AU2009200943B2 (en) | 2011-05-26 |
| AU2002356404A1 (en) | 2003-06-10 |
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