CN1204508A - 新的小核菌葡聚糖和包含新化合物的化妆品组合物 - Google Patents
新的小核菌葡聚糖和包含新化合物的化妆品组合物 Download PDFInfo
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- CN1204508A CN1204508A CN98115670A CN98115670A CN1204508A CN 1204508 A CN1204508 A CN 1204508A CN 98115670 A CN98115670 A CN 98115670A CN 98115670 A CN98115670 A CN 98115670A CN 1204508 A CN1204508 A CN 1204508A
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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Abstract
本发明提供了一种化妆品组合物,该组合物包含:A)一种化妆品上可接受的载体;以及B)0.05—3.0%(重量,基于整个组合物的重量)的、具有三维交联的三股螺旋结构的并且平均分子量为1×106—12×106的β-1,3-小核菌葡聚糖。
Description
本发明涉及新化合物,涉及产生新化合物的方法以及涉及包含新化合物作为活性成分的化妆品组合物。
在GB-A-2 050 825中,描述了水包油型的皮肤化妆品组合物,该组合物包含乳化剂、油和水,乳化剂由a)至少一种特定的甘草化合物以及b)至少一种选自果胶、刺梧桐胶、刺槐豆胶和黄原胶的水溶性多糖组成。
用于GB-A-2,050,825的多糖有一定的缺点,也就是说,它们含有酸性基团,该基团致使它们对盐的形成和/或pH的变化敏感并使它们在适当的温度范围之外缺乏稳定性。
在JP030167109中,描述了包含平均分子量大于10×106的β-1,3-葡聚糖的化妆品材料。然而,平均分子量大于10×106的β-1,3-葡聚糖有不良的一面,并且它们的分子量不能利用常规的光散射方法测定。
现在人们发现,某些新的小核菌葡聚糖能在化妆品组合物中用作为活性成分和用作为赋形剂,而没有与用于GB-A-2,050,825中的多糖相伴或者与JP030167109的β-1,3-葡聚糖相伴的缺点。此外,用于本发明组合物的小核菌葡聚糖,干燥时形成柔软的薄膜,该薄膜虽然在水中不能溶解,但是在水中易于膨胀。这一形成薄膜的能力为在化妆品配方中利用这些小核菌葡聚糖表达了一种附加的优点。此外,人们还发现新的小核菌葡聚糖显示出有价值的抗炎性质,这一性质使它们有价值,例如在用于治疗晒斑的晒后制剂中作为活性成分。
因此,作为第一个方面,本发明提供了一种化妆品组合物,该组合物包含:A)一种化妆品上可接受的载体;以及B)0.05-3.0%(优选的为0.2-1.0%)(重量,基于整个组合物的重量)的、具有三维交联的三股螺旋结构的、并且平均分子量为1×106-12×106(优选的为2×106-10×106)的β-1,3-小核菌葡聚糖。
化妆品组合物可以构成,例如香波和/或头发调理组合物,其中小核菌葡聚糖组分B)能够执行一种或多种下列功能:i)使利用香波/头发调理组合物处理过的头发的梳理性得到改善;ii)使香波/头发调理组合物中的其它组分的分散性得到改善;iii)作为利用香波/头发调理组合物处理过的头发的光滑剂;以及iv)使香波/头发调理组合物中的染料或UV吸收剂之类的添加剂的固定水平得到提高。
按照本发明的化妆品组合物也可以构成护肤组合物,例如乳剂或者乳膏,其中小核菌葡聚糖可以执行一种或多种下列功能:i)起润滑作用,藉此有利于上述组合物在皮肤上铺展;ii)充当薄膜形成剂,藉此在皮肤上提供一层保护膜,该保护膜给皮肤提供了一种柔软光滑的感觉而几乎不为触摸所察觉;iii)通过减少角质层最外层的大小使皮肤光滑;iv)在皮肤上产生抗炎效果;v)使护肤组合物的其它组分的分散性得到改善;以及vi)充当护肤组合物的乳化剂或者辅助乳化剂。
护肤组合物可以配制成含水洗剂,油包水或者水包油型乳剂,油或含油酒精洗剂,阴离子或非离子两亲性脂类的泡状分散剂,含水、含水酒精、酒精或含油酒精凝胶,固体条或气溶胶。
当配制成油包水或者水包油型乳剂时,化妆品上可接受的载体A)优选包含5-50%油相以及47-94.95%水,每一百分率均基于组合物的总重量。
油相可以包含任一为人们所知适合用于化妆品组合物中的油或者其混合物。
这样的油的例子包括如液态石蜡、角鲨烷、凡士林和地蜡之类的脂肪族烃;如橄榄油、杏仁油、芝麻油、鳄梨油、蓖麻油、可可脂以及棕榈油之类的植物油;如鲨鱼肝油、鳕鱼肝油、鲸油、牛油以及乳脂之类的动物油;包括蜂蜡、巴西棕榈蜡、鲸蜡以及羊毛脂的蜡;如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸以及山萮酸之类的脂肪酸;如月桂醇、硬脂醇、鲸蜡醇和油醇之类的脂肪醇;以及如异丙基-、异鲸蜡基-或十八烷基肉豆蔻酸酯,硬脂酸丁酯,月桂酸己酯,己二酸二异丙基酯或者癸二酸二异丙基酯之类的脂肪族酯。
优选用于含油酒精洗剂、或者含油酒精或者酒精凝胶中的单或多元醇包括乙醇、异丙醇、丙二醇、己二醇、甘油和山梨糖醇。
当β-1,3-小核菌葡聚糖用作为辅助乳化剂时,所使用的其它乳化剂可以是任一常规用于化妆品配方的乳化剂,例如:一种或更多种天然油衍生物的乙氧基酯(如氢化蓖麻油的聚乙氧基酯)、硅油乳化剂(如硅氧烷多元醇)、选择性乙氧基化的脂肪酸肥皂、乙氧基脂肪醇、选择性乙氧基化的脱水山梨醇酯、乙氧基脂肪酸、或者乙氧基甘油酯。
按照本发明的化妆品组合物可以构成抗炎护肤制品,特别是晒后(after-sun)护肤制品。
按照本发明的化妆品组合物也可以构成例如补齿凝胶(dental gel)、假牙固定助剂(denture fixation aid)或牙膏的护口制品,如***乳膏或者凝胶之类的粘膜润滑剂配方,或者如滴眼剂的眼科制剂,其中葡聚糖组分B)可以执行一种或多种下列功能:i)使干燥粘膜润滑;ii)使液态制剂变稠;iii)通过在粘膜表面上形成薄膜使活性成分保持;以及iv)组合物中的其它组分的分散性得到改善。
当β-1,3-小核菌葡聚糖用作眼科制剂时,它可以与如下的其它组分一道使用:a)眼科活性成分,例如硫酸庆大霉素、盐酸洛美沙星、氯霉素、双氯芬酸钠、双氯芬酸钾、磷酸二钠***、硝酸萘甲唑啉、盐酸四氢唑林、盐酸安他唑林、硫酸安他唑林、氯化匹鲁卡品萘甲唑啉、棕榈酸维生素A以及硫酸锌;b)眼科缓冲剂,例如硼酸、硼砂、乙酸、乙酸钠、磷酸、磷酸二氢钠、磷酸氢二钠、磷酸钠、氨丁三醇、柠檬酸和柠檬酸钠;c)眼科防腐剂,例如氯化苄基烷基铵、苯佐氯铵、二葡萄糖酸洗必泰、三氯叔丁醇、苯乙醇以及硫柳汞;d)溶剂,如乙醇、甘油、聚乙二醇和水或其混合物;e)溶解助剂,如Cremophor EL,Cremophor RH,Tween 20和Tween80;f)等渗剂,如氯化钠、山梨糖醇以及甘露糖醇;g)螯合物形成剂,如EDTA二钠;h)抗氧化剂,如醋酸α-维生素E、抗坏血酸、N-乙酰-胱氨酸、亚硫酸氢钠、硫代硫酸钠以及没食子酸丙酯;以及i)增粘化合物,如羟丙基甲基纤维素、蔗糖、Carbopol 934P、Carbopol940、Carbopol 980和Polaxomer F127。
按照本发明的化妆品组合物也可以用作为润滑剂。
本发明的化妆品组合物还可以包含已知在化妆品组合物中执行一种有用功能的组分。这样的其它组分的例子包括:例如润肤剂、皮肤增湿剂、如N,N′-草酰二苯胺的UV吸收剂、三嗪或***、如黄原胶的附加的增稠剂、如甘油的保温剂、成膜剂、防腐剂、香料和着色剂。
本发明的化妆品组合物的β-1,3-小核菌葡聚糖组分具有交联三股螺旋的三维结构,并且在它的结构中包含β-1,3-键合吡喃葡萄糖作为主链和β-1,6-键合吡喃葡萄糖作为侧链,并且具有结构式:其中n是提供平均分子量(MW)为1×106-12×106(优选为2×106-10×106)的β-1,3-小核菌葡聚糖组分的数目,该分子量由容易测量的Staudinger指数η、利用下列Mark-Houwink公式确定:MW=[η/4×45×10-7]1/1.49。
优选地,0.3g/l的β-1,3-小核菌葡聚糖水溶液具有低于0.1g/l的葡萄糖含量和50-190mPa.s的粘度(在0.3s-1的剪切速率和20℃温度下测量)。
平均分子量为1×106-12×106(优选为2×106-10×106)的、具有交联三股螺旋的三维结构的β-1,3-小核菌葡聚糖是一种新的组合物,并且构成了本发明的第二个方面。
β-1,3-小核菌葡聚糖的分子特征可以通过利用在合适溶剂(如0.01N含水氢氧化钠)中的不同聚合物浓度的光散射技术方便地进行鉴定。例如,贮存液可以产生自冻干的、粉末状的β-1,3-小核菌葡聚糖样品,然后可以在25℃下将贮存液搅动1-2天。然后可以确定静态和动态的光散射参数。从这些值中,可以得出回旋半径(Rg)与流体动力学半径(Rh)之比(Rg/Rh)。这一比值(Rg/Rh)用作试样形状的指示。
然后可以在25℃下,利用含水氢氧化钠或者二甲亚砜作为溶剂对贮存液的不同稀释样品进行粘度测量。进行粘度测量的合适仪器是应用Hagenbach校正的Ubbelohde-Capillary I(毛细管常数K=0.009693)。
这些分子鉴定技术的结果表明:新的β-1,3-小核菌葡聚糖在25℃下实际上是以三股螺旋连接的。
利用植物病原性半知菌整齐小核菌ATCC 15205,产生β-1,3-小核菌葡聚糖。这一方法构成本发明的第三个方面。
本发明方法的特征在于:在微需氧条件下的培养基中,培养植物病原性半知菌整齐小核菌ATCC 15205形式的微生物。
所使用的基础培养基可以是:美国专利3,301,848中描述的,包含碳源、如铵盐(或者优选硝酸钠)的氮源、如磷酸氢二钾三水合物的磷酸盐源、氯化钾、硫酸镁七水合物、硫酸铁七水合物以及酵母提取物的培养基。作为磷酸盐源的磷酸氢二钾三水合物的利用有其优点:它酸化了培养基,因而避免需要一种单独的酸来将培养基的pH值调整至大约2。
在优选的实施方案中,葡萄糖用作为碳源。将葡萄糖转化为β-1,3-小核菌葡聚糖、生物质、CO2以及草酸(唯一可检测到的副产物)。
将柠檬酸水合物(优选量为0.2-1.5g/l)、硫胺或其无机酸盐(优选量为0.3-30mg/l)以及如硫酸锌的锌盐(优选量为0.3-30mg/l)优选添加到基础培养基中。当酵母提取物本身是硫胺和锌源时,酵母提取物不能提供足量(足以提供所需的β-1,3-小核菌葡聚糖产物的最佳产量)的这些成分。
人们已经发现:通过减少所利用的氧量,所形成的CO2量和生物质量将减少,而所需要的β-1,3-小核菌葡聚糖的形成量则随之而增加。因此,利用0.01-0.08h-1范围之内的比摄氧率(基于生物质的摄氧率)实施本发明方法是优选的。
令人诧异的是:当摄氧率在培养过程期间连续不断地减少时,所需要的β-1,3-小核菌葡聚糖产物的产量将增加,以致氧对细胞供给的连续不断地恶化。一种可能的解释是:由于有机体优选微需氧环境,所以甚至“在活体内”,其本身也被粘液性皮层所围绕,该粘液性皮层大大地阻止了氧的传递。因此,在反应器中它的实际需氧量可能远低于微需氧供应量。这与观察到的结果是一致的:当增加供给反应器的氧量时,通过呼吸使氧极大量地用于消耗葡萄糖,结果导致生长速率增加和产率系数(每g小核菌葡聚糖的生物质g)减少。
优选地,利用限氮(nitrogen-limited)培养的预培养物(接种物)。令人惊人地发现:利用限氮预培养物作为培养接种物产生了一种改善的产物/生物质比。
通过限制培养基中的氮源量,需要的β-1,3-小核菌葡聚糖产物与生物质之比远大于利用标准接种物实施培养时所得到的比值。众所周知,在微生物多糖的产生期间,高的C/N比对产物浓缩有正效应。以前不曾报道过本发明的“反向氮限制”(反向是由于补加到培养基中的氮限制接种物培养,后来并不是氮限制的,因为后来的培养基中包含有足够的氮源)良好效应的发现。对“反向氮限制”良好效应的可能解释是:当有氮限制时,由于缺乏壳多糖(包含氮作为N-乙酰葡糖胺单位),有机体不能在细胞壁内部固定细胞壁多糖。因而,细胞壁多糖将较大程度地释放到培养基中。
因此,利用培养基中0.2-0.8gN/l范围内的氮源量实施本发明方法是优选的。
正如已经表明的,草酸是本发明方法中唯一可检测到的副产物。在本发明的培养过程中的pH值下降是与形成的草酸量成比例的。β-1,3-小核菌葡聚糖产物和生物质浓度不受本发明方法所采用的初始pH值影响。这一观察结果与以前的研究结果(其中有报道认为利用低于3的pH值实质上减少了产物和生物质的形成量)相反。由于此pH值限制不适用于整齐小核菌,按照本发明的培养方法能够在pH2下在完全非无菌的条件下(除酵母提取物单独灭菌外)操作。
优选地,在15-40℃下,通过搅拌进行按照本发明的培养过程;然后将培养液与大部分细胞分离;同时以常规方式分离所获得的β-1,3-小核菌葡聚糖产物。
利用半知菌整齐小核菌ATCC 15205的β-1,3-小核菌葡聚糖的微生物生产是与在培养期间在反应器中的培养基的粘度极大增加相联系的。此外,培养悬浮液显示出假塑性流动性质。有机体和β-1,3-小核菌葡聚糖产物都对剪切敏感。
当反应器尺寸增加时,充分混合高粘性培养基的重要性增加。混合程度的降低将导致培养期间生长速率和多糖形成的剧烈减少。为了在大反应器中达到充分混合,用高搅拌器速度进行操作是标准的做法。然而,在小核菌葡聚糖生产的情况下,反应器中的高平均剪切速率和最大搅拌器速度将使多糖降解。现在人们已经发现:采用很高的气化速率用差不多的时间能够达到同样好的混合效果。由此可见,气化主要承担完成培养基的轴向混合任务。高气化速率也确保高粘性反应器体积旋转直至培养结束。这样的不很剧烈的混合使高分子产物能够产生。搅拌装置使从细胞表面剪切下多糖的必要剪切得以完成。反应器中的平均剪切速率优选为18-25s-1,最大搅拌器速度优选为0.7-1.0m/s。此外,液体中高比例的气体导致了整个***密度的降低并因而降低了粘度。下列实施例将进一步说明本发明。实施例1
利用植物病原性、丝状生长(filamentary-growing)的真菌整齐小核菌ATCC 15205(获自ATCC,Rockville,MD,美国)进行培养。
下列标准培养基由以下物质组成:葡萄糖一水合物 38.5g/lNaNO3 3.0g/lKH2PO4 1.3g/l柠檬酸一水合物 0.7g/lKCl 0.5g/lMgSO4七水化合物 0.5g/lFeSO4七水化合物 0.05g/l硫胺素盐酸盐 3.3mg/lZnSO4七水化合物 3.3mg/l酵母提取物 1.0g/l初始pH 2.0
高压灭菌之前用85%磷酸调节标准培养基的pH值。在121℃和1巴的过压条件下消毒营养培养基20分钟。以灭菌过滤方式将硫胺素与ZnSO4溶液加入至培养基。此外,加1g/l的消泡剂至反应器培养液中。
对于第一种预培养物,100ml的上述标准培养基放置在装有挡板的500ml锥形瓶中进行消毒。然后将来自于一种琼脂斜面培养物的一片菌丝体接种在第一种预培养物上,在27℃、相对温度为40%的黑暗培养室中放置在100rpm振荡器上有氧培养一周。
对于第二种预培养物,500ml的上述标准培养基放置在装有挡板的2000ml锥形瓶中进行消毒。然后将5%(w/v)的第一种预培养物接种在消毒过的培养基上。由于在摇动的锥形瓶中在低剪切作用条件下整齐小核菌形成大菌球,所以有必要首先在无菌条件下使第一种预培养物匀浆化(20,000rpm,30s)。然后在上述的与培养第一种预培养物相同的条件下培养第二种预培养物3-4天。
培养在安装有4INTERMIG搅拌器的反应器中以200rpm搅拌速率、0.067v/vm气化速率进行,该反应器有下列尺寸:总体积 1500l工作体积 1000l内径 860mm总高度 2760mm填充高度 1800mm搅拌器直径 580mm搅拌器叶片直径 125mm流动缓冲器宽度 70mm流动缓冲器壁间距 17mm填充高度与内径比 2.1搅拌器直径与内径比 0.68
最大搅拌器速率是2.0m/s,平均剪切速率是50.0s-1。获得2.9g/ld的总生产力需要历时77h的过程,最终产物浓度为9.2g/l。表观粘度是29mPas(在多糖为0.3g/l、γ=0.3s-1下测量),多糖的分子量是3.0×106g/mol。利用五种不同聚合物浓度(以0.01N氢氧化钠水溶液为溶剂),通过光散射技术鉴定β-1,3-小核菌葡聚糖产物分子。通过溶解适量冻干的、磨碎的β-1,3-小核菌葡聚糖样品获得贮存液,并在25℃条件下搅拌各贮存液1-2天。然后可得静态和动态光散射数据。从这些数据可衍生出回旋半径(Rg)与流体动力学半径(Rh)的比(Rg/Rh),这一比值(Rg/Rh)成为试验样品形状的指示剂。存放11天之后,获得的比值(Rg/Rh)是0.87,该值与棒(>2)相比更接近于球形(0.76),第二个渗透维里系数(A2)为4×1×10-4cm3molg-2,描述了散射强度的浓度依赖性。
粘度测量是在25℃条件下利用氢氧化钠水溶液或者二甲亚砜作为溶剂对贮存液的不同稀释样品进行的。粘度测量所用仪器是UbbelohdeCapillary I(毛细管常数K=0.009693),通过Hagenbach法校正。
流变学测量是在25℃条件下用Bohlin CS-50流变计对β-1,3-小核菌葡聚糖样品进行的。圆筒***CS-25作为测量***。在四种不同聚合物浓度(0.5%,1%,1.5%和2%)下进行读数。所用的溶剂是水,其中加入2-苯氧基乙醇作为稳定剂。在分析之前所有溶液存放至少2周。然后在60℃条件下通过“Rotavap”蒸馏掉其中的水以浓缩溶液。
存放17天之后,β-1,3-小核菌葡聚糖的0.01N NaOH溶液的Staudinger指数η/100cm3/g是3.64,β-1,3-小核菌葡聚糖的二甲亚砜溶液的Staudinger指数η/100cm3/g是5.51。
这些结果确认β-1,3-小核菌葡聚糖有三维交联的三股螺旋结构。实施例2
利用实施例1所描述的过程,在实施例1相同的反应器中,以100rpm搅拌速率、1.0v/vm气化速率进行培养。最大的搅拌速率是1.0m/s,平均剪切速率是25.0s-1。获得3.1g/ld的总生产力需要历时98h的过程,最终产物浓度为12.6g/l。表观粘度(在多糖浓度为0.3g/l,γ=0.3下测量)是37mPas,同时多糖的分子量是4.1×106g/mol。
利用在实施例1所描述的条件,在25℃下用Bohlin CS-50流变计对实施例2的β-1,3-小核菌葡聚糖样品进行流变学测定。圆筒***CS-25作为测量***。在四种不同聚合物浓度(0.5%,1%,1.5%和2%)下进行读数。所用的溶剂是水,其中加入2-苯氧基乙醇作为稳定剂。在分析之前所有溶液存放至少2周。然后在60℃条件下通过“Rotavap”蒸馏掉其中的水以浓缩溶液。旋转测量法的剪切速率为20/s或者100/s。结果如下表所列。表1:
试验化合物的深度重量百分比 | 粘度η(mPas) | |
剪切速率20[l/s] | 剪切速率100[l/s] | |
0.5 | 231.6 | 57.16 |
1.0 | 573.5 | 138.2 |
1.5 | 1226.0 | 291.5 |
通过以较高剪切速率减小剪切粘度,结果表明试验化合物具有假塑性流动性质。为了使最终产品,例如化妆品系列的存放稳定性达到良好,就可以利用本发明中新的β-1,3-小核菌葡聚糖良好的增稠性质。这一性质与低剪切速率时新β-1,3-小核菌葡聚糖的流变学性质有关。高的存放稳定性也通过粘度增加完成,因为高存放稳定性值是在低的剪切速率下获得的。对于化妆品软膏来说,这种膏状物需要摩擦附着在皮肤上,可出现高到1000/s的剪切速率。为了获得膏状物在皮肤上最大限度的分布均一性,在这样高的剪切速率下膏状物的粘度必须低。表中的结果清楚地表明本发明的新的β-1,3-小核菌葡聚糖能够满足这些要求。实施例3
按摩乳膏由下列成分制成:
2%蜜蜂蜡
45%液态石蜡
3%鲸蜡醇
2.5%果胶(分子量100,000)
46.5%去离子水
0.2%羟苯甲酸甲酯
0.5%实施例1的β-1,3-小核菌葡聚糖
0.3%香料
每一重量百分比,都是基于乳膏的总重量而言。
通过将果胶、羟苯甲酸甲酯和葡聚糖均匀地溶解于80℃的去离子水中,制得第一种溶液。通过加热蜜蜂蜡、液态石蜡和鲸蜡醇混合物至80℃使其熔化,制得第二种溶液。当在混质混合机中搅动第一种溶液时,加入第二种溶液使其分散于第一种溶液中。冷却得到的乳状液,在达到70℃时,加入香料。搅拌混合物,一旦温度降至30℃即停止搅拌。所得的水包油型按摩乳膏具有良好的结构和光泽,可在2-60℃的条件下保持超过6个月以上的稳定。实施例4
由下列成分配制一种水性的眼科制剂:
1mg实施例1的β-1,3-小核菌葡聚糖
1mg双氯芬酸钠
50mg辅助溶液(Cremophor EL)
6mg眼科缓冲剂(氨丁三醇)
19mg硼酸
0.04mg眼科防腐剂(硫柳汞)
加注射目的用水至1.00ml。实施例5
用于治疗皮肤粗糙的水性洗剂是一种水性乳剂,包含10%(重量)的硬脂酸甘油酯和0.05%或者0.50%(重量)的实施例1的β-1,3-小核菌葡聚糖。
根据德国标准DIN 4768ff.方法确定皮肤的粗糙程度。皮肤的粗糙程度通过取硅氧烷基皮肤压痕,然后利用计算机辅助外形仪测量表面压痕的轮廓来确定。从若干的测量点(每平方毫米100个点)计算皮肤的粗糙程度。参加测试的志愿者10人。皮肤的粗糙程度测定既要在使用试验洗剂之前实施,又要在使用试验洗剂8小时后实施。前臂的皮肤作为皮肤试验区。为达到比较目的,利用安慰剂进行对照实验。
获得的结果表明:包含0.05%(重量)实施例1的β-1,3-小核菌葡聚糖的洗剂减弱皮肤粗糙度32%(相对未处理皮肤),含0.50%(重量)实施例1的β-1,3-小核菌葡聚糖的洗剂减弱皮肤粗糙度35%(相对未处理皮肤)。对照实验减弱皮肤粗糙度仅为22%(相对未处理皮肤)。实施例6
溶解于水的实施例1的β-1,3-小核菌葡聚糖(0.1%或者0.5%),其皮肤增湿活性的调查实验在所限定的气候条件下(22℃,相对湿度60%)进行。试液擦用于前臂。皮肤湿度等级测定在使用试液之前、使用1小时和8小时后进行。利用Corneometer(model CM820-Courage Khazuka,德国)进行测定。计算处理区皮肤相对于未处理皮肤的湿度增加百分比。志愿者人数10人。
使用1小时后的皮肤湿度增加量,对于0.1%的实施例1的β-1,3-小核菌葡聚糖水溶液为27%,对于0.5%的β-1,3-小核菌葡聚糖水溶液为29%。使用8小时后的皮肤湿度增加量,对于0.1%的实施例1的β-1,3-小核菌葡聚糖水溶液为17%,对于0.5%的β-1,3-小核菌葡聚糖水溶液为22%。
这些结果表明实施例1的β-1,3-小核菌葡聚糖能够强烈、迅速增加皮肤湿度。在使用试验产品8小时后,0.5%的溶液显示了其在皮肤上极好的持久保水性。这种持久保水效果优于使用0.1%透明质酸或者0.25%胶原蛋白作为活性成分所产生的效果。实施例7
调查溶解于水的(0.1%)实施例1的β-1,3-小核菌葡聚糖的抗炎活性。
在研究开始前三天,要求五位志愿者停止在试验皮肤区上使用化妆品。通过暴露在紫外灯(Ultra-Vitalux灯;Osram)下在志愿者背部诱发几个紫外红斑。应用的能量相当于1.5倍的最小-红斑剂量(MED),对于每一个志愿者这在诱发红斑之前确定。立即使用试验化合物和在辐射照射6小时后使用试验化合物。在以后5天内,红斑每天用试验产品处理两次。利用色度计(Minolta)在第一次使用试验产品24小时、72小时及120小时后测定红斑的红色程度。
24小时后,与未处理的对照的红斑比较,红色减弱17%;在72小时后减弱23%;在120小时后减弱31%。这些结果类似于,事实上在120小时后优于比较试验中利用已知的抗炎剂D-泛醇(用作2.0%的洗剂)或芦荟(10%1∶1凝胶)所得结果。利用0.5%实施例1的β-1,3-小核菌葡聚糖水溶液洗剂,与未处理对照红斑比较,在120小时之后红色减弱40%,这远远超过利用D-泛醇(用作2.0%的洗剂)或芦荟(10%1∶1凝胶)的观察值。实施例8:漱口液配方
成分:0.03-0.1%(重量) 三氯苯氧氯酚10-20%(重量) 酒精(食品级乙基醇)5-10%(重量) 甘油1-2%(重量) 表面活性剂,例如聚山梨酯20/Poloxymer407/月桂基硫酸钠0.02-0.05%(重量) 糖精钠0-0.05%(重量) 氟化钠适量 食用香料适量 色料达100% 去离子水调整pH至5-71-5%(重量) 实施例1的β-1,3-小核菌葡聚糖。
制备方法:三氯苯氧氯酚溶解于酒精,然后作为溶液加入表面活性剂。甘油和大约20%水加入该溶液。然后加入所有其它成分搅拌直到均匀。接着加水至100%。调节pH值并搅拌直到溶液变得清澈。
如果三氯苯氧氯酚不能完全溶解,酒精和/或表面活性剂的含量必须增加。实施例9:牙膏配方
成分:0.1-0.3%(重量) 抗牙龈炎/抗菌剂,如三氯苯氧氯酚,0.1-1.0%(重量) 抗龋剂,如氟化钠、氟基磷酸钠,1.0%(重量) 胶凝剂,如羧甲基纤维素、羟乙基纤维素或者黄原胶,10-20%(重量) 保湿剂,如甘油、70%的山梨糖醇或者丙二醇,15-20%(重量) 研磨剂,如碳酸钙、水合硅石、磷酸二钙二水合物或氧化铝,0.1-0.2%(重量) 增甜剂如糖精,1.0-1.5%(重量) 食用香料,如荷兰薄荷、胡椒薄荷、薄荷醇或香草醛,1.0-2.0%(重量) 表面活性剂,如月桂基硫酸钠、十二烷基硫酸钠、十二烷基肌氨酸钠或十二烷基磺基乙酸钠0.1-0.5%(重量) 防腐剂,如羟苯甲酸酯适量 色料达100% 水5-10%(重量) 实施例1的β-1,3-小核菌葡聚糖。
Claims (21)
1.一种化妆品组合物,该组合物包含:
A)一种化妆品上可接受的载体;以及
B)基于整个组合物重量的0.05-3.0%、具有三维交联的三股螺旋结构的并且平均分子量为1×106-12×106的β-1,3-小核菌葡聚糖。
2.按照权利要求1的组合物,该组合物包含:
A)一种化妆品上可接受的载体;以及
B)基于整个组合物重量的0.2-1.0%、平均分子量为2×106-10×106的β-1,3-小核菌葡聚糖。
3.按照权利要求1或2的组合物,其中上述组合物构成香波和/或头发调理组合物。
4.按照权利要求1或2的组合物,其中上述组合物是护肤组合物。
5.按照权利要求4的组合物,其中上述护肤组合物被制成一种含水洗剂,一种油包水或水包油型乳剂,一种油或含油酒精洗剂,一种阴离子或非离子两亲性脂类的泡状分散剂,一种含水、含水酒精、酒精或含油酒精凝胶,一种固体条或气溶胶。
6.按照权利要求5的组合物,其中,在油包水或水包油型乳剂中,化妆品上可接受的载体A)包含5-50%的油相和47-94.95%的水,每一百分率均基于整个组合物重量。
7.按照任一上述权利要求的组合物,其中上述组合物也包含一或更多种润肤剂、皮肤增湿剂、UV吸收剂、附加的增稠剂、保湿剂、成膜剂、防腐剂、香料和着色剂。
8.按照权利要求1的组合物,其中上述组合物构成抗炎护肤制剂。
9.按照权利要求8的组合物,其中上述抗炎护肤制剂是晒后护肤制剂。
10.按照权利要求1的组合物,其中上述组合物构成口腔防护制剂、粘膜润滑剂配方或者包含载体的眼科制剂。
11.一种具有三维交联的三股螺旋结构的、并且平均分子量为1×106-12×106的β-1,3-小核菌葡聚糖化合物。
12.一种具有三维交联的三股螺旋结构的并且平均分子量为2×106-10×106的β-1,3-小核菌葡聚糖化合物。
13.生产按照权利要求11的β-1,3-小核菌葡聚糖化合物的方法,包含在培养基中在微需氧条件下培养植物病原性半知菌整齐小核菌ATCC15205。
14.按照权利要求13的方法,其中所利用的基础培养基包含碳源、氮源、磷酸盐源、氯化钾、硫酸镁七水合物、硫酸铁七水合物以及酵母提取物。
15.按照权利要求14的方法,其中上述氮源是硝酸钠,磷酸盐源是磷酸氢二钾三水合物。
16.按照权利要求13-15之任一的方法,其中上述碳源是葡萄糖。
17.按照权利要求13-16之任一的方法,其中添加到基础培养基中的是柠檬酸水合物、硫胺或者其无机酸盐、以及锌盐。
18.按照权利要求17的方法,其中添加到基础培养基中的柠檬酸水合物量为0.2-1.5g/l、硫胺或者其无机酸盐量为0.3-30mg/l、以及锌盐量为0.3-30mg/l。
19.按照权利要求13-18之任一的方法,其中利用0.01-0.08h-1范围之内的比摄氧率(基于生物质的摄氧率)实施上述方法。
20.按照权利要求13-19之任一的方法,其中上述氮限制预培养物用作为接种物。
21.按照权利要求13-20之任一的方法,其中在15-40℃下通过搅拌实施上述方法,然后将培养液与大部分细胞分离,同时分离所获得的β-1,3-小核菌葡聚糖产物。
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GB9714102.2 | 1997-07-04 | ||
GBGB9714102.2A GB9714102D0 (en) | 1997-07-04 | 1997-07-04 | Compounds |
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US (2) | US6162449A (zh) |
EP (1) | EP0891768A3 (zh) |
JP (1) | JPH1171405A (zh) |
KR (1) | KR19990013555A (zh) |
CN (1) | CN1112915C (zh) |
AR (1) | AR015923A1 (zh) |
AU (1) | AU746969B2 (zh) |
BR (1) | BR9802347A (zh) |
CZ (1) | CZ211298A3 (zh) |
GB (1) | GB9714102D0 (zh) |
ID (1) | ID20586A (zh) |
IL (1) | IL125179A (zh) |
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CN111346053A (zh) * | 2018-12-21 | 2020-06-30 | 浙江立恩生物科技有限公司 | 具有生物活性的天然乳化剂及应用 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104069024A (zh) * | 2013-03-26 | 2014-10-01 | 上海家化联合股份有限公司 | 一种增稠剂组合物及其在化妆品中的应用 |
CN104069024B (zh) * | 2013-03-26 | 2017-03-08 | 上海家化联合股份有限公司 | 一种增稠剂组合物及其在化妆品中的应用 |
CN111346053A (zh) * | 2018-12-21 | 2020-06-30 | 浙江立恩生物科技有限公司 | 具有生物活性的天然乳化剂及应用 |
CN110448471A (zh) * | 2019-08-22 | 2019-11-15 | 苏州绿叶日用品有限公司 | 一种纳米纤维美白面膜及其制备方法 |
Also Published As
Publication number | Publication date |
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AU746969B2 (en) | 2002-05-09 |
IL125179A0 (en) | 1999-03-12 |
US6369217B1 (en) | 2002-04-09 |
EP0891768A3 (en) | 2000-11-08 |
AR015923A1 (es) | 2001-05-30 |
AU7417198A (en) | 1999-01-14 |
GB9714102D0 (en) | 1997-09-10 |
NZ330721A (en) | 1999-11-29 |
EP0891768A2 (en) | 1999-01-20 |
KR19990013555A (ko) | 1999-02-25 |
ZA985874B (en) | 1999-01-18 |
TW482678B (en) | 2002-04-11 |
ID20586A (id) | 1999-01-21 |
JPH1171405A (ja) | 1999-03-16 |
CZ211298A3 (cs) | 1999-01-13 |
US6162449A (en) | 2000-12-19 |
BR9802347A (pt) | 2000-01-11 |
CN1112915C (zh) | 2003-07-02 |
IL125179A (en) | 2003-04-10 |
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