CN1126942A - 稳定的油包水乳状液 - Google Patents
稳定的油包水乳状液 Download PDFInfo
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- CN1126942A CN1126942A CN95190312A CN95190312A CN1126942A CN 1126942 A CN1126942 A CN 1126942A CN 95190312 A CN95190312 A CN 95190312A CN 95190312 A CN95190312 A CN 95190312A CN 1126942 A CN1126942 A CN 1126942A
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- emulsion
- oil
- water
- emulsion according
- emulsifying agent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/174—Vitamins
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/179—Colouring agents, e.g. pigmenting or dyeing agents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/189—Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
-
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Abstract
本发明描述了稳定的油包水乳状液,乳状液含有如下成分:水,油,一种不稳定化合物,一种稳定剂和一种乳化剂。通过加入优选的多元醇稳定剂使在水相中的不稳定化合物稳定。本发明描述了特定的乳化剂,此乳化剂在大量的多元醇存在情况下能产生稳定的乳状液。
Description
本发明描述了稳定的油包水乳状液。此乳状液用于向饲料、食品或化妆品组合物中加入不稳定化合物。
用于食品、饲料和化妆品的几种添加剂被认为是不稳定的,例如着色剂、维生素、疫苗或酶。
添加剂与组合物中其他化合物可能是化学不相容的或酶不相容的。另外,添加剂可能是热不稳定的,因此,在升温过程中可能会失活。例如,饲料或食品经常经挤压过程来制备。为了得到所需形状的食品或饲料颗粒,挤压过程是非常必要的。此外,有一种增长的趋势,那就是基本的饲料或食品含有各种添加剂。饲料或食品组合物更经常的是由各种添加剂构成,这些添加剂以前是单独使用的。
已建议采用几种办法解决不稳定化合物降解的问题。一种办法是在提高的温度下,在一个工序之后,例如挤压工序之后,加入所需化合物。关于不稳定化合物的成分和向食品或饲料中加入这种化合物的方法,已经有不同的报道。
DE 26 02260描述了酶悬浮液在一种液体或一种熔融食用脂肪中的应用。混合物冷却后,原料必须粒化。经过粗略破坏后,颗粒可进一步处理例如,通过碾磨。此过程的缺点是,保证小颗粒尺寸而进行的粉剂研磨非常费时而且会导致粉尘出现。
国际专利申请WO 93/14645解决了这个问题,在挤压过程后,加入含热不稳定化合物的油悬浮液。在降低的压力下向颗粒中加入悬浮液。
国际专利申请WO 92/06599描述了用于保护疫苗的油包水乳状液的应用。没有提到作为乳状液一部分的(蛋白质)稳定剂(即水活性低的)的使用。不稳定化合物,例如酶,在这样的乳状液中会导致酶活性很快的损失。在热的天气里这种损失每月可能达到50%,这对于商业产品来说是不可接受的。此专利申请也描述了基于卵磷酯的乳化剂的优选应用。
国际专利申请WO 93/16175描述了含有作为稳定剂的脲和/或多元醇的稳定的含水酶溶液。脲和多元醇是熟知的用于稳定水环境中酶的稳定剂。
在化妆品领域,也有一个增长的趋势,即在含有最后产物的油中含有不稳定化合物。用于皮肤防护,清洁和恢复活力的化合物显然是令人感兴趣的。不稳定化合物在这方面有着有益的效果,包括酶,例如蛋白酶。
为了在延长的存放期内保证化妆品成分中酶的活性,基本不含水、疏水化合物例如蜡,植物或矿物油常用于酶配制剂中。尽管这种方法预示了在化妆配制品中酶的高贮藏稳定性,一个严重缺点是,只有通过把配制品置于大量水中,酶才能活化。(在此过程中,最初的不含水的酶被溶解)。一个随之而来的问题是酶活性比较低,浪费了大量的初始酶活性。这种方法在几种化妆品应用中不太方便。
J03004791中描述的一种可替代方法中,通过把多糖加入酶水溶液中使要在化妆品中使用的蛋白分解酶稳定。尽管这种方法能够用最少量的水使酶重新活化,但此法不考虑在化妆品配方中使用亲油相。
本发明公开了稳定的油包水乳状液。特别的是,本发明公开一种油包水乳状液,其特征是,乳状液含有下列成分:水、油、所研究的一种不稳定化合物、一种稳定剂和一种乳化剂。
本发明的油包水乳状液含有溶解于水相中、通过加入稳定剂使其稳定的不稳定化合物,优选稳定剂是一种水活性降低剂,更优选多元醇。多元醇以高浓度加入油包水乳状液的水相中,即至少占总量的10%,优选10-70%,最优选30~70%(重量百分比)。
优选的组成包括油包水乳状液,水相中不稳定化合物与多元醇共存,乳状液用乳化剂稳定,乳化剂在高浓度的多元醇下是有活性的。优选使用的乳化剂是蒸馏过的单酸甘油酯或聚甘油聚蓖麻油酸酯。
此外,所研究的化合物优选是酶、维生素、着色剂或疫苗。
本发明的乳状液可用于保护加入到食品、饲料、化妆品或油性组合物之前的不稳定化合物。
本发明的油包水乳状液在更长的期间内是稳定的。它们可以用于制备人类或动物食物。例如,本发明的油包水乳状液被喷洒到食品或饲料颗粒上。优选乳状液在油或脂肪中稀释后再喷洒到饲料或食品颗粒上。另外,本发明的乳状液可用于化妆品组合物的制备。
本发明公开了一种油包水乳状液,乳状液的水相中含有所研究的一种不稳定化合物和一种稳定剂,用一种适当的乳化剂稳定乳状液。
油包水乳状液含有以下成分:水,油,所研究的一种不稳定的化合物,一种稳定剂和一种乳化剂。不稳定化合物存在于水相中。稳定剂加到水相中以稳定所需的化合物。
不稳定化合物可以是任何一种化合物,此化合物与其它化合物在化学上或酶学上是不相容的。不相容的化合物可以存在于乳状液中或存在于加入了乳状液的组合物中。另外,不稳定化合物可以是任何热不稳定化合物。
本发明公开了在水相中含有不只一种不稳定化合物的稳定油包水乳状液。本发明还公开了另一种稳定的油包水乳状液,此乳状液在水相中含有一种不稳定化合物和一种与不稳定化合物不相容的化合物。本发明能够制备含有互不相容的水溶性化合物的乳状液。通过不相容化合物并入乳状液油相中的单个水滴,可完成不相容化合物的物理分离。
不稳定化合物优选含有例如可以做为前生命期的微生物。不稳定化合物更优选酶、维生素、着色剂或疫苗。合适的酶包括蛋白酶、植酸酶、糖酶、脂肪酶、磷脂酶和氧化还原酶。合适的维生素包括水溶性维生素,例如维生素C。
本发明的乳状液对配制互不相容的化合物,例如,其中之一是蛋白水解酶的酶混合物,是特别有用的。
此外,本发明的乳状液能够使不稳定化合物有准确的剂量。首先是因为不稳定化合物的稳定性能够保证,另外是因为液体乳状液的剂量,特别是稀释在油中的乳状液的剂量,比粉剂的剂量更准确。例如,在饲料加工过程中,象热、压力、湿度、氧化还原反应和摩擦等因素可能会对维生素稳定性有惊人的影响,这是众所周知的。特别是维生素E、维生素K和维生素C(抗坏血酸)的不稳定性是众所周知的(例如,参见M.B Coelho,Feed International,December 1991,p39-45)。抗坏血酸是水溶性的,对象铁这样经常加到饲料中的痕量矿物质是极其敏感的。抗坏血酸并入到本发明的油包水乳状液的水相对于尽量减少维生素用量是很有吸引力的选择。
本发明的油包水乳状液包括含有高浓度所需化合物的水相。以0.01-30%(重量比,以活性化合物的干重计)的量向水相中加入此化合物。
通过向水相中加入稳定剂使不稳定化合物稳定。优选水活性降低剂作稳定剂。优选的水活性降低剂是盐,更优选的是多元醇。特别适用的多元醇是甘油、山梨醇、蔗糖、聚丙二醇、海藻糖、麦芽糖糊精、乳糖和葡萄糖。
另外,水活性降低剂有抑制乳状液水相中微生物生长的作用。如果需要,可以通过与苯甲酸酯和山梨酸酯这样可被接受的(食物级)抗菌剂的结合,提高水相的微生物稳定性。
水活性降低剂加到水相中的量取决于达到所需稳定效果或抗菌效果所要求的剂量。加入水相中多元醇至少为10%,优选10~70%,更优选30~70%(重量百分比)。
使用乳化剂以获得稳定的乳状液。乳化剂是表面活性物质,能够使一种液相分散到另一种液相中。乳化剂含有亲水基和亲油基,亲水基和亲油基的比值称为HLB值。
一般地,脂溶疏水乳化剂的HLB值范围为0-9,而水溶性物质的HLB值在11和20之间。用于稳定油包水乳状液的合适的乳化剂或乳化剂混合物的HLB值要求在较低的范围内。
令人吃惊的是,大家熟知的乳化剂,例如SpanTM 80(HLB=4.3),TweenTM 80(HLB=15)及其混合物在相对较多的多元醇存在情况下没有产生稳定的油包水乳状液。基于卵磷脂的乳化剂,象EmulbestoTM 200,EmulfluidTM E同样会导致快速分相。
本发明首次描述了在较多的多元醇存在情况下有活性的乳化剂。已发现了在高达50%多元醇存在情况下仍有效的乳化剂。
适用的乳化剂是单酸甘油酯(例如HymonoTM1163和HymonoTM8704)和聚甘油聚蓖麻油酸酯(AdmulTM WOL 1403)。由于所选择的乳化剂在较多的多元醇存在情况下的有效性,油相中单个水滴的聚结是很少的。这样,本发明的乳状液可适当阻止非油溶化合物在乳状液单个水滴之间的迁移。
聚甘油聚蓖麻油酸酯(AdmulTM WOL 1403)与植酸酶结合是非常有用的。
聚甘油聚蓖麻油酸酯在室温下是液体,在与油混合前或混合过程中不需要加热。使用聚甘油聚蓖麻油酸酯时,乳状液的粘度仍然很低,而且几乎不发生液滴絮凝。另外,使用聚甘油聚蓖麻油酸酯允许在乳状液中有高浓度的水相。
本发明乳状液所用的油是在食品、饲料或化妆品制备中常用的油。包括鱼油、豆油、菜子油、橄榄油、玉米油、棕榈油、鳄梨油和不同的矿物油。
本发明进一步公开了油包水乳状液的制备方法。
制备乳状液需输入大量的能量。例如通过剧烈的搅拌或通过很大的剪切力。用这种方法,可得到稳定的乳状液,乳状液可以此形式稳定地贮藏。
本发明公开了在长期贮存中保持稳定的乳状液。乳状液在一个月贮存期内是稳定的,更优选6个月贮存期是稳定的,最优选超过一年。
本发明的油包水乳状液可以做为食品、饲料或化妆品的添加剂。
使用本发明的乳状液能够使食品、饲料或化妆品生产厂家把不稳定化合物应用于用其它方法将导致不稳定化合物失活的工序。而且,使用本发明的乳状液适当地防止了非油溶化合物从饲料、食品或化妆品组合物迁移到乳状液的水相。这样,所研究的存在于乳状液水相中的不稳定化合物被适当地保护,避免了加入了乳状液的组合物中存在的化学不相容性或酶不相容性。
本发明的乳状液用于人食品或动物饲料颗粒的制备,特别是用于鱼或家禽饲料颗粒的制备。优选通过喷洒将乳状液加到食品或饲料颗粒上。象在国际专利申请WO 93/14645中描述的那样,乳状液的加入可以在减压情况下操作。
乳状液可以照这样应用于食品或饲料颗粒。优选在加入食品或饲料前,乳状液在油或脂肪中稀释。这个方法的一个优点是,浓缩的不稳定化合物可以容易地(即输入能量低)均匀地与油混合。用这种方法,能够保证活性化合物在油中的均匀分配。然后可将含有稀释过的所需化合物的油喷洒到食品或饲料颗粒上。在制备要喷洒到颗粒上的最终混合物方面,此方法所需投资最少。
在另一个应用中,本发明的乳状液可用于改善酱油和菜子油的脱胶。此情形中,乳状液含有磷脂酶A2。脱胶是从指定的油中除去卵磷脂。在EP 0513 709中,磷脂酶用于脱胶已经有详尽描述。这种酶可以改善非水合磷脂酶的水溶性,促进它们从油中除去。本发明的油包水乳状液便于磷脂酶加入到指定油中。
下面提出一些实施例,它们只是用于说明本发明绝不用来限制本发明的范围。
实施例1
使用不同乳化剂和不同酶的油包水乳状液的物理稳定性1a.
酶溶液的组成
用食品级中性蛋白酶和饲料级植酸酶说明各种油包水乳状液的稳定性。
蛋白酶标准溶液含有溶于80克水中的20克蛋白酶B500(Gist-brocades,Holland)。完全溶解后,加入山梨醇或甘油,溶解以达到标明的浓度。植酸酶标准溶液含有粗发酵浓缩物(NatuphosR UF浓缩物,通过超滤无菌的曲酶属培养物滤液获得)或含有含40%山梨醇的标准发酵产品Natuphos5000(Gist-brocades,Holland)。在各种实验中使用的植酸酶溶液,含有最终浓度在35~50%之间的甘油或山梨醇。1b.
用Span TM 80/Tween TM 80混合物制备的乳状液0.5克SpanTM 80或TweenTM 80乳化剂(两者都来自Brocacef,the Netherlands)加入到5克鱼油(毛鳞鱼油,从Skretting,Norway获得)中。另外,制备了含有不同比率上述SpanTM 80和TweenTM 80溶液的乳化剂混合物。彻底混合后,加入0.18克上述稳定过的酶溶液,接着进行充分漩流。
含有与各种SpanTM 80和/或TweenTM 80乳化剂中的一种乳化剂结合的蛋白酶或植酸酶的乳状液,在室温下,几小时内显示出了油层和水层的分离。1c.
用基于卵磷脂的乳化剂制备的乳状液
EmulbestTM 2000,EmulfluidTM E和VP627都是基于卵磷脂的乳化剂,得自Lucas Meyer,Germany。经过1b中已概括的步骤后,用0.5克上述每种基于卵磷脂的乳化剂制备乳状液。在几个小时内,用这些乳化剂产品制备的乳状液就显示出了油层和水层的分离。1d.
用单酸甘油酯乳化剂制备的乳状液
HymonoTM 1163和HymonoTM 7804得自Quest,Holland。
在慢慢搅拌下,在温度为70℃(对HymonoTM 1163)或50℃(对HymonoTM 7804)下,24克HymonoTM(一种单酸甘油酯;E471)溶解于700克鱼油中。随后,溶液至少冷却到50℃,用高速均化器(Ultra Turrax)将200克酶溶液分散到含乳化剂的油相中,乳状液冷却到室温。几天以后,水相中只有少量沉积物。通过加入棕榈酸可使沉积物最少。1e:
用聚甘油聚蓖麻油酸酯制备乳状液
AdmulTM WOL 1403(聚甘油聚蓖麻油酸酯)得自Quest,Holland。与不稳定化合物结合,这种乳化剂有其它优点,事实上AdmulTM WOL1403在室温下是液体,很容易在油相中溶解。这就不需要加热油,使得处理更加容易,不稳定化合物可以在室温下加到油/乳化剂的混合物中,因此,使热应力最小。
为了用AdmulTM WOL 1403制备乳状液,把3克AdmulTM WOL1403与87.5克鱼油混合,接着加入25克Natuphos5000(用50%山梨醇稳定)。乳状液的粘度仍然很低,水相液滴大小大约为2μ,而且没有液滴缔合作用发生。这表明了在这个体系中,AdmulTM WOL1403具有很好的乳化性能。乳状液的低粘度能够允许浓度高得多的含酶水相存在于最终的乳状液中。
把AdmulTM的量从3克增加到9克,乳化75克Natuphos5000液体在87.5克鱼油中的混合物似乎是可能的。至少在6个月内,此乳状液是物理稳定的。就凝絮作用而言,含植酸酶的AdmulTM乳状液优于HymonoTM乳状液,而且物理稳定性更高(参见表1)。表 1 HymonoTM 1163和 AdmulTM WOL 1403乳状液的物理参数
和特性的比较
物理参数和特性 | HYMONO 1163 | ADMUL WOL |
溶解乳化剂的温度 | 70℃ | 室温 |
加酶过程中的温度 | 50℃ | 室温 |
制备乳状液所需能量 | 高 | 低 |
乳状液的粘度 | 中等 | 低 |
液滴絮凝作用 | 中等 | 低 |
液滴大小 | 2-10μ | 2μ |
乳状液中水相的最大浓度 | 约22%(w/w) | 约44%(w/w) |
实施例2
中性蛋白酶油包水乳状液中的酶活性溶液A:
在慢慢搅拌下,5克喷雾干燥的蛋白酶B500制剂溶解在20克软化水中。用甘油稀释蛋白酶溶液,使甘油最终浓度为50%。溶液B:
在70℃、慢慢搅拌下,6克HymonoTM 1163溶解于175克鱼油中。随后,将溶液冷却到50℃。
使用高速均化器,把溶液A分散于溶液B中。将乳状液冷却到室温。
蛋白酶油包水乳状液的蛋白酶活性大约为17,000U/g乳状液。蛋白酶从溶液A和从油包水乳状液中的回收率大约为90%,这表明乳化作用对蛋白质分解活性没有显著的不利影响。25℃或35℃下保持的乳状液贮藏稳定性示于表2。
表2 蛋白酶乳状液制品的贮藏稳定性
时间(周) | 蛋白水解活性 | 液滴直径μ | ||||
25℃ | 35℃ | |||||
U*/g乳状液 | % | U*/g乳状液 | % | 25℃ | 35℃ | |
0 | 16,926 | 100 | 16,926 | 100 | 2-10 | 2-10 |
1 | 12,078 | 71 | 14,719 | 87 | 2-10 | 2-10 |
2 | 19,957 | 118 | 17,446 | 103 | --- | --- |
3 | 17,056 | 101 | 14,892 | 88 | --- | --- |
4 | 15,281 | 90 | 14,113 | 83 | --- | --- |
5 | 14,848 | 88 | 12,468 | 74 | --- | --- |
6 | 15,844 | 94 | 7,143 | 42 | 2-10 | 2-10 |
7 | 13,420 | 79 | 10,736 | 63 | --- | --- |
5(月) | --- | -- | --- | -- | 2-15 | --- |
实施例3
稳定的植酸酶油包水乳状液中的酶活性溶液A:
在慢慢搅拌下,100克山梨醇溶解于100克NatuphosUF浓缩物中。溶液B:
在70℃、慢慢搅拌下,24克HymonoTM1163溶解在700克鱼油中。随后,溶液冷却至50℃。
使用高速均化器,把溶液A分散于溶液B中。乳状液冷却到室温。
植酸酶活性从溶液A和植酸酶油包水乳状液中的回收率大约为90%。这说明,乳化作用对酶的植酸降解活性没有不利影响。用如EP 0 420 358所述方法测定植酸酶活性。
25℃或35℃下保持的乳状液贮藏稳定性示于表3。
表3 植酸酶乳状液制品的贮藏稳定性
时间(周) | 植酸酶活性 | 液滴直径μ | ||||
25℃ | 35℃ | |||||
U*/g乳状液 | % | U*/g乳状液 | % | 25℃ | 35℃ | |
0 | 531 | 100 | 531 | 100 | 2-10 | 2-10 |
1 | 623 | 117 | 569 | 107 | 2-10 | 2-10 |
3 | 494 | 93 | 654 | 123 | --- | --- |
4 | 616 | 116 | 528 | 99 | --- | --- |
5 | 523 | 98 | 337 | 63 | --- | --- |
6 | 513 | 97 | 451 | 85 | 2-10 | 2-15 |
7 | 295 | 56 | 380 | 71 | --- | --- |
5(月) | --- | -- | --- | -- | 2-10 | --- |
*一个植酸酶活性单位定义为,37℃、pH5.50下以1μmol/min速率从1.5mM肌醇六磷酸钠释放无机磷的酶量。
实施例4
使用聚甘油聚蓖麻油酸酯的稳定的植酸酶和蛋白酶油包水乳状 液的制备4a.
植酸酶/油乳状液
3.0克或9.0克AdmulTM W 1403溶解在87.5克鱼油中,于是在2*30秒期间内在全速下使用Ultra Turrax,用75.0克含50%山梨醇的Natuphos5000来制备乳状液。用40%山梨醇稳定的Natuphos,在使用了另外的山梨醇后,已达到含山梨醇为50%。结果,计算的活性将是4100U/g而不是5000U/g。乳状液的破碎:
将乳状液缓慢深冻,直至-20℃为止,在这个温度下保持20小时。然后,让乳状液的温度回升到室温,在20,000转/分钟下,在Sorvall离心器中(SM 24个转子),乳状液被离心分离30分钟。在此处理过程中,温度为20-25℃。
这时,含有3.0克乳化剂的乳状液分成3层,即清澈的油层,薄的中间相和清澈的水层。在水层内,测得植酸酶活性为3750U/g,表明植酸酶活性回收率至少为90%。
含有9.0克乳化剂的乳状液不能采用离心法分离。在室温下,至少在6个月期间内,此乳状液可以保持稳定。这与在实施例1中描述的植酸酶乳状液的高稳定性是一致的。4b.
蛋白酶/油乳状液
用上述对植酸酶/油乳状液所用的同样方法,使在50%山梨醇溶液中的87.5克鱼油、3.0克AdmulTM WOL 1403(溶解在鱼油中)和75.0克蛋白酶B500的混合物变得均匀。出乎意料的是,蛋白质分解酶与AdmulTM WOL乳化剂结合产生的乳状液,同蛋白酶B500与HymonoTM乳化剂(见实施例2)结合产生的乳状液稳定性相比,此乳状液显示出了降低的稳定性。显然,在制备蛋白酶B500乳状液中,将优选HymonoTM乳化剂。
实施例5
植酸酶在含蛋白酶的乳状液中的稳定性
为了表明乳状液对不相容化合物的保护效果,制备了含植酸酶和酸性蛋白酶的油包水乳状液。本实施例表明,在水相中含有植酸酶或蛋白酶的乳状液混合物,比在同一水相中含两种混合酶的乳状液更稳定。原料Natuphos UF浓缩液(用通过稀释得自Freres,France的70%山梨醇溶液而得到的50%山梨醇溶液稳定)。Fromase150 TL(一种源于米黑毛霉(Mucor miehei)的液体酸性蛋白酶,得自Gist-brocades)AdmulTM WOL 1403(得自Quest,Holland)。鱼油(毛鳞鱼油,得自Skretting,Norway)。5a.
Natuphos /油乳状液
按实施例4中已述方法,把6克AdmulTM WOL溶解在87.5克鱼油中,随后把75克NatuphosUF浓缩物与此鱼油强烈混合而得到乳状液。乳状液在20℃下保存。第一个样品立刻在-20℃下冷冻。5b.
Fromase /油乳状液
2毫升Fromase150 TL加到含50%山梨醇的98毫升水中。通过混合87.5克鱼油、6克AdmulTM WOL和75克Fromase溶液制备标准乳状液。乳状液在20℃下保存。5c.
混合的乳状液
乳状液(5a)和(5b)制备完毕后,通过立刻把100毫升Natuphos/油乳状液加到100毫升Fromase/油乳状液中制备混合的乳状液。彻底地手动混合后,混合物在20℃下贮存。第一个样品立即在-20℃下冷冻。5d.
Natuphos -Fromase /油乳状液
750微升的FromaseTL加到含山梨醇的75克NatuphosUF浓缩物中,然后混合。加入87.5克含6克AdmulTM WOL的鱼油,紧接着强烈混合,制得所需乳状液。乳状液在20℃下贮藏。第一个样品立刻在-20℃下冷冻。5c.
植酸酶在各种乳状液中的稳定性
各种乳状液在20℃保存,经过5天和10天贮藏后取出样品,立刻在-20℃下冷冻。在-20℃下至少一夜后,把各样品解冻,然后如实施例4中所述进行离心分离。通过得自水层的样品测定植酸酶活性。假设得自Natuphos/油乳状液(5a)的各样品的活性为100%,分别经过5天和10天贮藏后,记录下列植酸酶活性。
在混合的乳状液(5c)中:分别具有94%和96%的初始植酸酶活性。
在Natuphos-Fromase油乳状液(5d)中:分别具有80%和78%的初始植酸酶活性。
考虑到由于山梨醇的存在,Fromase的蛋白水解活性较低,数据表明乳状液增加了合成的不稳定化合物的稳定性。当与蛋白酶分别被乳化时,植酸酶被保护以防止蛋白水解的作用。
实施例6
维生素C在具有化学不相容性饲料中的稳定性
除了在同一乳状液中使用两种不相容酶的实施例中所观察到的稳定效果以外,在把维生素C(抗坏血酸)与饲料颗粒接触时,也观察到类似的效果。
有许多文献证明了抗坏血酸和象铜、铁这样痕量矿物质的不相容性(例如参见CRC Handbook of Food Additives,second edition,page85及其以后内容)。然而,对某一饲料的应用,例如烤焙精制饲料,营养学家建议铁与抗坏血酸结合使用。本实施例说明,混合到乳状液里的抗坏血酸比与烤焙精制饲料颗粒混合后没有乳化的抗坏血酸更稳定。原料:
豆油(由OPG Farma,Holland精炼)。
AdmulTM WOL 1403甘油86%柠檬酸(一水合物p.a.)抗坏血酸(p.a.)烤焙精制饲料(得自Arkervaart,Holland)6a.
抗坏血酸和柠檬酸的水溶液
通过在45克软化水中溶解1克柠檬酸和4克抗坏血酸来制备水相。所得到的水溶液混合物的pH约为2.4。完全溶解后,加入50克甘油,混合物被充分混合。6b.
抗坏血酸/油乳状液
按实施例4中所述方法,把3克AdmulTM 1403溶解在87.5克豆油中,再加入75克6a中所述的水相,可制得一种稳定的乳状液。6c.
抗坏血酸/油乳状液在脂肪中的稀释
在油或液化的脂肪中稀释后再使用这些乳状液。稀释后的乳状液被喷洒到颗粒状或挤压成形的饲料上。为使乳状液与脂肪混合,把100毫升乳状液(6b)加入100毫升豆油中,然后,液体被用手工充分地混合。6d.
抗坏血酸/脂肪乳状液和抗坏血酸水溶液与烤焙精制饲料的混 合
不论是从抗坏血酸脂乳状液开始,还是从抗坏血酸水溶液开始,等量的抗坏血酸(最终浓度为200ppm)加到烤焙精制饲料颗粒上,此烤焙精制饲料颗粒来源于本地供应商。为此,把200毫升油乳状液喷洒到10千克在混凝土混合器中旋转的饲料颗粒上。同样,把50毫升含水抗坏血酸混合物(6a)喷洒到10千克在混凝土混合器中旋转的饲料颗粒上。然后,把另外100毫升豆油喷洒到这些饲料颗粒上。喷洒并立刻取样后,对样品进行抗坏血酸和脱氢抗坏血酸分析。6e.
在烤焙精制饲料中的抗坏血酸分析
用如Methods of Biochemical Analysis and Food Analysis using Sin-gle Reagents(Boehringer Mannheim,1989)中所述的脱氢抗坏血酸/抗坏血酸检验方法,分析抗坏血酸和脱氢抗坏血酸。
用10毫升丙酮萃取10克颗粒10分钟(用于溶解脂肪物质),随后加入90毫升含1克/升的乙底酸钠的软化水。把饲料颗粒与水相在Ultra Turrax混合1分钟后,把样品离心分离。使用试剂盒NO.409677(Boehringer Mannheim),测定上清液中的抗坏血酸和脱氢抗坏血酸的水平。
从被喷洒了含水抗坏血酸的饲料颗粒中,可以回收20%的抗坏血酸。相反,从用稀释过的抗坏血酸。相反,从用稀释过的抗坏血酸/油乳状液喷洒的饲料颗粒中,90%的抗坏血酸得到回收。这表明,在饲料制备中乳状液对抗坏血酸稳定性具有保护作用。
Claims (13)
1.一种油包水乳状液,其特征是,它包含下列成分:水,油,一种不稳定化合物,一种稳定剂和一种乳化剂。
2.一种根据权利要求1的乳状液,其特征是,稳定剂是水活性降低剂。
3.一种根据权利要求1的乳状液,其特征是,稳定剂是多元醇。
4.一种根据权利要求3的乳状液,其特征是,多元醇选自乙二醇、山梨醇、蔗糖、聚丙二醇、乳糖、海藻糖、麦芽糖糊精和葡萄糖。
5.一种根据权利要求3或4的乳状液,其特征是,多元醇在乳状液水相中的浓度至少为10%,优选的浓度为10-70%,更优选的浓度为30-70%(重量百分比)。
6.一种根据权利要求1的乳状液,其特征是,乳化剂选自能产生油包水乳状液的乳化剂。
7.一种根据权利要求3至5任一权项的乳状液,其特征是,在高浓度的多元醇存在情况下,乳化剂是有活性的。
8.一种根据权利要求6或7的乳状液,其特征是,乳化剂选自单酸甘油酯和聚甘油聚蓖麻油酸酯。
9.一种根据权利要求1的乳状液,其特征是,不稳化合物选自酶、维生素、疫苗和着色剂。
10.一种根据权利要求9的乳状液,其特征是,酶选自蛋白酶、糖酶、脂肪酶、磷脂酶、氧化还原酶和植酸酶。
11.将一种根据权利要求1至10中任一权项的乳状液用于人或动物的食物或者化妆品的制备。
12.含有一种根据权利要求1至10中任一权项的乳状液的人或动物的食物或者化妆品。
13.一种用于处理食物和饲料颗粒的方法,其特征是,用含有不稳定化合物的稳定的油包水乳状液喷洒到颗粒上。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP94201067.9 | 1994-04-18 | ||
EP94201067 | 1994-04-18 |
Publications (1)
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CN1126942A true CN1126942A (zh) | 1996-07-17 |
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CN95190312A Pending CN1126942A (zh) | 1994-04-18 | 1995-04-18 | 稳定的油包水乳状液 |
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EP (1) | EP0703730B1 (zh) |
JP (1) | JP3751634B2 (zh) |
KR (1) | KR960702733A (zh) |
CN (1) | CN1126942A (zh) |
AT (1) | ATE210386T1 (zh) |
AU (1) | AU2308395A (zh) |
CA (1) | CA2165157C (zh) |
DE (1) | DE69524517D1 (zh) |
DK (1) | DK0703730T3 (zh) |
ES (1) | ES2169129T3 (zh) |
FI (1) | FI955962A (zh) |
NO (1) | NO313312B1 (zh) |
PL (1) | PL177022B1 (zh) |
TW (1) | TW305768B (zh) |
WO (1) | WO1995028092A1 (zh) |
ZA (1) | ZA953120B (zh) |
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CN102480997A (zh) * | 2009-08-31 | 2012-05-30 | 阿尼托克斯公司 | 一种改进的对动物饲料进行调质的方法 |
CN103039697A (zh) * | 2012-12-04 | 2013-04-17 | 广州海因特生物技术有限公司 | 一种减少水产膨化饲料中水溶性维生素溶失的方法 |
CN103525797A (zh) * | 2012-07-03 | 2014-01-22 | 深圳市绿微康生物工程有限公司 | 液体脂肪酶保护剂及其制备方法和应用 |
CN103540554A (zh) * | 2013-11-01 | 2014-01-29 | 广州市博仕奥生物科技有限公司 | 一种膨化饲料后喷微生态制剂及其制备方法与应用 |
CN106061293A (zh) * | 2014-03-05 | 2016-10-26 | 帝斯曼知识产权资产管理有限公司 | 液体乳糖酶组合物 |
CN107080054A (zh) * | 2017-03-31 | 2017-08-22 | 浙江大学 | 一种油包水型饲用液体酶制剂的制备方法 |
US10980251B2 (en) | 2011-06-26 | 2021-04-20 | Anitox Corporation | Cold weather formulation for conditioning animal feed |
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EP0756457B2 (en) * | 1994-04-22 | 2008-10-08 | Novozymes A/S | A method for improving the solubility of vegetable proteins |
DE19724605A1 (de) * | 1997-06-11 | 1998-12-17 | Sueddeutsche Kalkstickstoff | Hydrophile, homogene Monogycerid-Formulierungen und Verfahren zu deren Herstellung |
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ES2204105T3 (es) | 1998-01-08 | 2004-04-16 | Cosmoferm B.V. | Aplicacion local de enzimas utilizando una pelicula susceptible de desprendimiento. |
KR100517072B1 (ko) * | 2002-11-25 | 2005-09-26 | 주식회사 태평양 | 폴리올/고분자 마이크로캡슐 및 이를 이용한 효소 안정화방법 |
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BRPI0516881A (pt) * | 2004-11-03 | 2008-09-23 | Du Pont | composição repelente de insetos |
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CN103549160A (zh) * | 2013-11-01 | 2014-02-05 | 广州市博仕奥生物科技有限公司 | 一种膨化饲料后喷酶及其制备方法与应用 |
JP7492513B2 (ja) | 2019-07-01 | 2024-05-29 | 旭化成ファーマ株式会社 | フェロシアン化物の酸化還元電位を大きくするプロテアーゼの安定化剤を含む糖化タンパク質測定試薬、糖化タンパク質の測定方法、糖化タンパク質測定試薬の保存方法、及び糖化タンパク質測定試薬の安定化方法 |
KR20230029260A (ko) * | 2021-08-24 | 2023-03-03 | (주)아모레퍼시픽 | 효소 손상을 방지하는 화장료 조성물 및 이를 저장하는 화장품 용기 |
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- 1995-04-18 CA CA002165157A patent/CA2165157C/en not_active Expired - Fee Related
- 1995-04-18 AU AU23083/95A patent/AU2308395A/en not_active Abandoned
- 1995-04-18 CN CN95190312A patent/CN1126942A/zh active Pending
- 1995-04-18 ZA ZA953120A patent/ZA953120B/xx unknown
- 1995-04-18 AT AT95916672T patent/ATE210386T1/de active
- 1995-04-18 ES ES95916672T patent/ES2169129T3/es not_active Expired - Lifetime
- 1995-04-18 WO PCT/EP1995/001461 patent/WO1995028092A1/en active IP Right Grant
- 1995-04-18 DE DE69524517T patent/DE69524517D1/de not_active Expired - Lifetime
- 1995-04-18 DK DK95916672T patent/DK0703730T3/da active
- 1995-04-18 JP JP52673595A patent/JP3751634B2/ja not_active Expired - Fee Related
- 1995-04-18 EP EP95916672A patent/EP0703730B1/en not_active Expired - Lifetime
- 1995-04-18 PL PL95312245A patent/PL177022B1/pl unknown
- 1995-06-28 TW TW084106723A patent/TW305768B/zh active
- 1995-12-06 KR KR1019950705508A patent/KR960702733A/ko not_active Application Discontinuation
- 1995-12-13 FI FI955962A patent/FI955962A/fi unknown
- 1995-12-15 NO NO19955118A patent/NO313312B1/no unknown
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102480997A (zh) * | 2009-08-31 | 2012-05-30 | 阿尼托克斯公司 | 一种改进的对动物饲料进行调质的方法 |
CN102480997B (zh) * | 2009-08-31 | 2013-05-29 | 阿尼托克斯公司 | 一种改进的对动物饲料进行调质的方法 |
US10980251B2 (en) | 2011-06-26 | 2021-04-20 | Anitox Corporation | Cold weather formulation for conditioning animal feed |
CN103525797A (zh) * | 2012-07-03 | 2014-01-22 | 深圳市绿微康生物工程有限公司 | 液体脂肪酶保护剂及其制备方法和应用 |
CN103039697A (zh) * | 2012-12-04 | 2013-04-17 | 广州海因特生物技术有限公司 | 一种减少水产膨化饲料中水溶性维生素溶失的方法 |
CN103039697B (zh) * | 2012-12-04 | 2014-05-07 | 清远海贝生物技术有限公司 | 一种减少水产膨化饲料中水溶性维生素溶失的方法 |
CN103540554A (zh) * | 2013-11-01 | 2014-01-29 | 广州市博仕奥生物科技有限公司 | 一种膨化饲料后喷微生态制剂及其制备方法与应用 |
CN103540554B (zh) * | 2013-11-01 | 2015-06-17 | 广州市博仕奥生物科技有限公司 | 一种膨化饲料后喷微生态制剂及其制备方法与应用 |
CN106061293A (zh) * | 2014-03-05 | 2016-10-26 | 帝斯曼知识产权资产管理有限公司 | 液体乳糖酶组合物 |
CN107080054A (zh) * | 2017-03-31 | 2017-08-22 | 浙江大学 | 一种油包水型饲用液体酶制剂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
FI955962A0 (fi) | 1995-12-13 |
JPH08512359A (ja) | 1996-12-24 |
ZA953120B (en) | 1996-01-11 |
NO313312B1 (no) | 2002-09-16 |
NO955118L (no) | 1995-12-15 |
EP0703730A1 (en) | 1996-04-03 |
AU2308395A (en) | 1995-11-10 |
CA2165157A1 (en) | 1995-10-26 |
PL177022B1 (pl) | 1999-09-30 |
ES2169129T3 (es) | 2002-07-01 |
PL312245A1 (en) | 1996-04-01 |
DK0703730T3 (da) | 2002-04-02 |
ATE210386T1 (de) | 2001-12-15 |
NO955118D0 (no) | 1995-12-15 |
WO1995028092A1 (en) | 1995-10-26 |
KR960702733A (ko) | 1996-05-23 |
EP0703730B1 (en) | 2001-12-12 |
DE69524517D1 (de) | 2002-01-24 |
JP3751634B2 (ja) | 2006-03-01 |
TW305768B (zh) | 1997-05-21 |
FI955962A (fi) | 1995-12-13 |
CA2165157C (en) | 2007-06-12 |
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