CN1142504A - 氟化胶束酪蛋白 - Google Patents
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Abstract
本发明涉及制备氟化酪蛋白胶束的方法,其中至少100ppm的可溶性氟化物盐被加入到含胶束酪蛋白的溶液中,所氟化的胶束酪蛋白被分离出来。本发明还涉及含有效量氟化胶束酪蛋白或其胶束亚单元的用于治疗龋齿或斑牙的食品或药用组合物。
Description
本发明的主题是牛奶酪收白的氟化以及氟化酪蛋白作为治疗牙病的药剂的用途。
在保健中已有人提出用含氟盐如含氟化钠的牛奶减少龋齿的发生(Beddows G.等人,Analyst,106,1341-1344,1981)。
此外,其它研究表明大多数氟化物以游离离子的形式平衡存在于牛奶中,只一小部分被乳钙络合。因此氟化物没有象所需的那样和乳蛋白质相络合。特别是没有和胶束酪蛋白相络合(Beddows G等,J.FdTechnology,17,55-62,1982)。
此外,已知在胶束酪蛋白溶液中,氟盐的过量能通过由氟化物提供的额外的离子强度的作用将胶束酪蛋白分成其胶束亚单元(Carroll等,J.Dairy Science,54,752,1971)。
最后,EP 604802表明胶束酪蛋白具有抗龋齿活性,同时EP283675表明出现在酪蛋白胶束表面的κ-酪蛋白葡糖肽也具有抗龋齿和斑牙的活性。
本发明的目的是提供能用于人及动物口腔卫生的新的胶束酪蛋白衍生物。
为此,在按照本发明的氟化酪蛋白胶束的制备过程中,将至少100ppm的可溶氟化物盐加到含酪蛋白胶束的溶液中,并将这种氟化胶束酪蛋白分离出来。
本发明也涉及包含有效量的氟化胶束酪蛋白或其胶束亚单元的用于治疗牙病的食品或药用组合物。
最后,本发明也涉及氟化胶束酪蛋白或其氟化胶束亚单元用于制备治疗牙病的组合物的用途。
本发明已出乎意料地首次使得保护胶束结构的氟化胶束酪蛋白的制备成为可能。
因此氟化物可无论如何在没有破坏胶束的结构情况下与胶束结合。因此本发明和已知的科学知识相矛盾,已知知识表明氟化物依其浓度不同会破坏胶束或实际上不和乳蛋白形成络合物,乳胶束酪蛋白的情况尤其如此(Beddows G.等,J.Fd Technology,1755-56,1982)。
按照本发明的氟化胶束酪蛋白进一步和大量的氟化物络合。观察到20%以上,甚至50%的最初游离的氟化物与酪蛋白络合已确实成为可能,从而允许考虑将它们作为抗斑牙剂、防龋齿剂、抗牙周病剂和抗牙过敏剂用在人或动物的口腔卫生中。
进行本发明的工作可将例如来自于动物如奶牛母羊的奶或所述奶液含胶束酪蛋白的组分用作含胶束酪蛋白的溶液。但是最好保证有足量和维持胶束结构的重要化合物如柠檬酸盐存在于所述组分中,但应该指出当动物乳被微滤、超滤或diafiltered时,这些化合物和含胶束酪蛋白的组分相分离,并分离出端留物。
然后将至少100ppm的水溶性氟化物盐加到该溶液中。可溶性氟化物盐可选自例如氟化钠和氟磷酸钠。所述氟化物盐最好在5至70℃的温度下和所述溶液混合1分钟至5小时以促进氟化物和胶束酪蛋白的络合。要制备保持了胶束结构的氟化酪蛋白,可将100至2000ppm的可溶液氟化物盐加入到所述溶液中。另一方面,如果需要制备氟化酪蛋白的胶束亚单元,可将例如2000ppm以上的可溶性氟化物盐加入到所述溶液中。
最后,在氟化物盐混入到动物乳中后,可通过所述乳的微量过滤、滤和/或diafiltered来将胶束或亚胶束氟化酪蛋白分离。最好,这种乳液在孔径约为0.1-0.2μm的矿物膜上微滤。另一方面,在动物乳组分已混入了氟化物盐后,可能上必进一步纯化氧化酪蛋白,因为其浓度已达到足够高的水平。
然而,通过将分离出的氟化酪蛋白的组合干燥例如喷雾干燥来制取主要由氟化酪蛋白(其中的氟已与胶束或胶束亚单元络合)组成的粉剂是有利的。
按照本发明的氟化胶束酪蛋白具有和原乳胶束酪蛋白一样的胶束立体结构。胶束和氟化物间的相互反应表现为稳定的离子反应;但是也不排除其它类型的相互作用(如物理吸附、共价键)。
和氟络合的胶束酪蛋白亚单元也具有有利的结构。这些亚单元是由聚集的与氟分子络合的酪蛋白构成的。因为它们含有κ-酪蛋白葡糖肽,而酪蛋白葡糖肽和氟化物均已知具有防龋齿和斑牙活性,所以这些氟化胶束亚单元也潜在地具有显著的抗龋齿和斑牙活性。
因此本发明也涉及氟化胶束酪蛋白或其胶束亚单元在制备用于治疗龋齿或斑牙的组合物的用途。因此氟化胶束酪蛋白和其亚单元可在预防和/或治疗龋齿、斑牙和牙周炎和牙过敏症中使用。
为此,制备出含有效量氟化胶束酪蛋白或其亚单元的可接受的食品或药品组合物,人或动物均口服给药。
制备时,这种组合物可通过将例如至少0.1%的按本发明的氟化酪蛋白加入到食品或药品组合物中来制取。也可考虑直接将至少0.1%的含胶束酪蛋白粉和至少100ppm的可溶性氟化物盐的混合物加入到具有液体或至少是浆体稠度的食品药物用组合物中。因此按照本发明的氟化酪蛋白也可以制造食品或药品时制备。
因此按照本发明的组合物是含有效量氟化胶束酪蛋白或其亚单元的食品或药用组合物,这里所说的足量,一般是指重量的0.1-90%,但最好是1-20%,可抑制龋齿和斑牙细菌如Actinomyces naeslundii属、Actinomyces Viscosus属、Streptococcus sanguis属,Streptococcusmutans属和/或Streptococcus sobrinus属的细菌的附着。
按照本发明的组合物另外可依最终产品的形式和用途的不同包括本领域技术人员所熟知的常规组分。对于主要为食物的用途,所述组合物可制成糖果品如甜饮料或能被发酵的乳液。对于主要为药物的用途,所述组合物可制成如牙膏,香口胶或漱口剂。
如果制成牙膏,所述组合物可另外包括湿润剂液体、粘合剂或稠化剂、研磨料,表面活性剂和调味剂。因此所述组合物可包括例如10-85%的湿润剂液体如乙二醇,山梨醇,丙二醇或乳糖醇糖浆,0.1-10%的粘合剂或稠化剂如羰甲基纤维素纳、黄蓍胶或硅胶,0.5-5%的不与胶束或胶束亚单元结合的表面活性剂,和至少3%的研磨剂如硅石、碳酸钙、无水磷酸二钙或羟基磷灰石。
按照本发明的组合物也可包括其它可选的组分;例如防斑剂和/或杀菌剂和洗必太,2,4,4’-三氯-2’-羟基二苯醚,锌化合物、碱金属焦磷酸盐、氟化钠或氟磷酸钠;甜味剂如糖精;不透明剂如二氧化钛;着色剂;维持适当pH的缓冲剂如苯甲酸或其盐。最好选择pH大于5的缓冲液以避免胶束的离解。
下面提供多个实施例以说明按照本发明的组合物和用途及其制备方法。在这些实施例中,除非另有说明,份数和百分数均以重量计。
实施例1
通过在孔径为约0.2μm的矿物膜上微滤牛奶来制备胶束酪蛋白溶液,然后将其喷雾干燥。
要测定氟在胶酪蛋白浮液中的分布,先制备20%(重量)胶束酪蛋白的水溶液。此外应指出该悬浮液含200ppm的游离钙。
将58.25mg氟化钠加入到100g胶束溶液中(即600ppm),将该溶液搅拌一小时后在100000g超速离心90分钟。然后将离心颗粒用蒸馏水洗涤,分散在水中后进行冷冻干燥。在胶束中保留的氟的量用Beddows G.等的方法(Analyst,106,1341-1344,1981)测定。
在实施例2的表中所示结果表明59.13%以氟化钠形式加入的氟被发现在超过离心时和胶束一起存在。此外,离心颗粒的颜色和均一程度表明了胶束的存在。胶束结构可通过电子显微镜来证实。已知氟化钠一般在100000g下不沉淀,因此结果趋向于表明包括例如物理吸附、离子交换和/共价键合等机制结合到胶束的氟化物。
这些结果和常规技术知识是矛质的,常规知识表明氟化乳超速离心后80%以上,甚至95%的氟化物留在溶液中,同时氟和乳蛋白的络合受高于10ppm的游离钙的抑制(Beddows G.et al.,J.Fd.Technology,-1755-56,1982)。
实施例2
将30g氟磷酸钙加入到100g实施例1的胶束溶液中(即300ppm),将溶液搅拌一小时后在100000g超速离心90分钟。然后将离心颗粒用蒸馏水清洗,分散在水中后进行冷冻干燥。保护在胶束中的氟的量通过实施例述及的方法测定。
下表说明实施例1和2的实验结果。
实施例 | 1)胶束+NaF | 2)胶束+NaF6F |
最初溶液的重量(g) | 100 | 100 |
粉末状最初胶束的重量(g) | 10.108 | 10.097 |
所加入的氟化物(mg/100g液体) | 26.47 | 20.36 |
超滤后的粉状胶束 | 6.66 | 7.12 |
氟化物含量分析值(mg/100g粉状胶束) | 235 | 112 |
氟化物含量计算值(mg/100g液体) | 15.65 | 7.97 |
计算出的氟化物/加入的氟化物(%) | 59.13 | 39.17 |
结果表明当氟化后的溶液超速离心时,39.13%的氟磷酸钠形式的加入的氟化物被发现和胶束一起存在。此外,离心颗粒的颜色和均一程度也呈现胶束存在的特性。其胶束结构由电子显微镜证实。已知氟磷酸钠在100000g下一般不沉淀,因此结果趋于表明了靠可能包括例如物理吸附、离子交换和/或共阶键合等机制结合到胶束上的氟化物。
实施例3
除了加入到胶束溶液中的氟化钠是1000ppm外,按实施例1和2描述的方法制备氟化胶束酪蛋白粉。
实施例4
通过将1000ppm的氟磷酸钠加入到消毒后的牛奶中、将牛奶在室温均化10分钟后在孔径为0.2μm膜上将所述牛奶超滤、然后将滤渣喷雾干燥来制备氟化胶束酪蛋白粉。
实施例5
制备氟化胶束酪蛋白亚单元粉,步骤为:将消毒后的牛奶在孔径约0.2μm的矿物膜上微滤,然后将滤渣用水稀释而获得含胶束酪蛋白20%的溶液。在该溶液中加入300ppm的氟化钠,均化几分钟后喷雾干燥。这些得到的粉可有利地用于制备治疗牙病的食品和药品组合物。
要证实氟化胶束亚单元的存在,先制备含氟化胶束亚单元粉20%的溶液,然后在100000g下离心。离心颗粒的颜色和稠度呈现出胶束解离成其亚单元的特征。这种微粒结构可通过电子显微镜证实。此外,离心颗粒可用蒸馏水洗涤,分散在水中,冷冻干燥后分析其氟含量。其结果表明这些获得的粉氟含量特别高。
实施例6
制备去除牙垢和预防龋齿的牙膏。所述牙膏含5%碳酸钙、10%硅石气溶胶(Gasil23)、40%山梨醇浆、1%羧甲基纤维素钠、6.5%在实施例4中获得的氟化酪蛋白粉、0.2%糖精钠、1%二氧化钛、0.04%福尔马林、1%调味剂,其余部分为水。
实施例7
除了5%的氟化酪蛋白胶束粉用5%在实施例5中获得的酪蛋白胶束亚单元粉代替外,制备和实施例5所述的同样的牙膏。
实施例8
制备用于预防龋齿和治疗牙周病和牙过敏症的漱口剂。这种漱口剂含10%在实施例4中获得的氟化酪蛋白胶束粉,0.1%苯甲酸、0.2%糖精钠、0.1%喹啉黄、0.15专利蓝、3%95%的乙醇。其余为水。
Claims (7)
1.制备氟化酪蛋白胶束的方法,其中将至少100ppm的可溶性氟化物盐加到含胶束酪蛋白的溶液中,并分离出氟化后的胶束酪蛋白。
2.按照权利要求1的方法,其中制备了含至少10%(重量)胶束酪蛋白的乳液,加入100-2000ppm特别选自氟化钠和氟磷酸钠的可溶性氟化物盐,并分离出氟化胶束酪蛋白。
3.按照权利要求1的方法,其中制备了含至少10%(重量)胶束酪蛋白的乳液,加入2000ppm以上特别选自氟化钠和氟磷酸钠的可溶性氟化物盐,并分离出氟化胶束酪蛋白亚单元。
4.氟化胶束酪蛋白。
5.按照权利要求4的酪蛋白,通过至少一种选自氟化钠和氟磷酸钠的可溶性氟化物氟化。
6.含有效量氟化胶束酪蛋白或其胶束亚单元的用于治疗龋齿或斑牙的食品或药用组合物。
7.氟化胶束酪蛋白或其胶束亚单元在制备治疗龋齿或斑牙用的组合物中的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95201618A EP0748591B1 (fr) | 1995-06-16 | 1995-06-16 | Caséines micellaires fluorées |
EP95201618.6 | 1995-06-16 |
Publications (2)
Publication Number | Publication Date |
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CN1142504A true CN1142504A (zh) | 1997-02-12 |
CN1137138C CN1137138C (zh) | 2004-02-04 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CNB961061839A Expired - Fee Related CN1137138C (zh) | 1995-06-16 | 1996-06-14 | 氟化胶束酪蛋白 |
Country Status (14)
Country | Link |
---|---|
US (1) | US5833953A (zh) |
EP (1) | EP0748591B1 (zh) |
JP (1) | JP3902264B2 (zh) |
CN (1) | CN1137138C (zh) |
AT (1) | ATE206877T1 (zh) |
AU (1) | AU706125B2 (zh) |
CA (1) | CA2178982A1 (zh) |
DE (1) | DE69523294T2 (zh) |
ES (1) | ES2163472T3 (zh) |
FI (1) | FI962471A (zh) |
NO (1) | NO962497L (zh) |
NZ (1) | NZ286802A (zh) |
PT (1) | PT748591E (zh) |
ZA (1) | ZA965102B (zh) |
Families Citing this family (23)
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AUPO566297A0 (en) * | 1997-03-13 | 1997-04-10 | University Of Melbourne, The | Calcium phosphopeptide complexes |
US5853704A (en) * | 1997-09-22 | 1998-12-29 | Colgate-Palmolive Company | Fluoride dentifrices of enhanced efficacy |
AUPP494798A0 (en) * | 1998-07-29 | 1998-08-20 | Pacific Biolink Pty Limited | Protective protein formulation |
AU751234B2 (en) * | 1998-07-29 | 2002-08-08 | Pacific Biolink Pty Limited | Casein formulations for the delivery of bioactive constituents |
AU2006201048B2 (en) * | 1998-07-29 | 2008-04-24 | The University Of Melbourne | Formulation for the delivery of bioactive constituents |
JP2002522036A (ja) | 1998-08-07 | 2002-07-23 | ソシエテ デ プロデユイ ネツスル ソシエテ アノニム | 抗齲触(虫歯)性の乳製品およびその使用 |
EP1159951A1 (en) * | 2000-06-02 | 2001-12-05 | Societe Des Produits Nestle S.A. | Use of exogenous lactic bacteria strain against Actinomyces naeslundii-related diseases |
BR9912946A (pt) | 1998-08-12 | 2001-05-08 | Nestle Sa | Incorporação de bactérias lácticas exógenas à microflora oral |
WO2002100181A2 (en) * | 2001-06-08 | 2002-12-19 | Societe Des Produits Nestle S.A. | Sugar-based composition containing caseinoglycomacropeptide |
NZ574520A (en) * | 2002-11-27 | 2011-02-25 | Dmi Biosciences Inc | Use of casein which is at least 10% dephosphorylated for the treatment of diseases and conditions mediated by increased phosphorylation |
JP2006520601A (ja) * | 2003-03-18 | 2006-09-14 | ネステク ソシエテ アノニム | 動物の健康を増進するための方法及び組成物 |
ES2755277T3 (es) | 2006-02-09 | 2020-04-22 | Univ Melbourne | Composición de fluoruro y métodos para mineralización dental |
EP1844758B1 (en) * | 2006-03-27 | 2010-06-30 | Nestec S.A. | Cosmetic use of whey protein micelles |
US20090311329A1 (en) * | 2006-04-20 | 2009-12-17 | Technion Research And Development Foundation Ltd | Casein micelles for nanoencapsulation of hydrophobic compounds |
US8865222B2 (en) * | 2008-02-11 | 2014-10-21 | Technion Research And Development Foundation Ltd. | Beta-casein assemblies for enrichment of food and beverages and methods of preparation thereof |
WO2009101613A1 (en) * | 2008-02-11 | 2009-08-20 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Beta-casein assemblies for mucosal delivery of therapeutic bioactive agents |
US20110045092A1 (en) * | 2008-02-11 | 2011-02-24 | Livney Yoav D | Casein particles encapsulating therapeutically active agents and uses thereof |
US8871276B2 (en) | 2008-02-11 | 2014-10-28 | Technion Research And Development Foundation Ltd. | Beta-casein assemblies for mucosal delivery of therapeutic bioactive agents |
AU2013202191A1 (en) * | 2012-06-20 | 2014-01-16 | Massey University | Micronutrient Fortification Process and its Uses |
AU2014232456B2 (en) * | 2013-03-15 | 2018-11-15 | Glanbia Nutritionals (Ireland) Ltd. | Product and method for improving bioavailability of therapeutic compounds |
SG11201600137UA (en) | 2013-07-23 | 2016-02-26 | Univ Melbourne | Compositions and methods for dental mineralization |
KR102273906B1 (ko) | 2013-12-24 | 2021-07-06 | 더 유니버시티 오브 멜버른 | 안정화된 제1주석 조성물 |
MX2019010832A (es) | 2017-03-14 | 2019-10-30 | Univ Melbourne | Tratamiento para la gingivitis. |
Family Cites Families (7)
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CH671879A5 (zh) | 1987-02-26 | 1989-10-13 | Nestle Sa | |
JPS646213A (en) * | 1987-06-27 | 1989-01-10 | Sangi Kk | Composition for preventing denting caries |
DE4007431A1 (de) * | 1990-03-09 | 1991-09-12 | Henkel Kgaa | Den zahnschmelz schuetzende mund- und zahnpflegemittel |
GB9117315D0 (en) * | 1991-08-09 | 1991-09-25 | Unilever Plc | Method of controlling dental tartar and compositions for use therein |
US5227154A (en) * | 1991-08-22 | 1993-07-13 | The University Of Melbourne | Phosphopeptides for the treatment of dental calculus |
CA2138991C (en) * | 1992-06-29 | 2007-01-30 | Eric C. Reynolds | Treatment for sensitive teeth |
CH684773A5 (fr) | 1992-12-28 | 1994-12-30 | Nestle Sa | Composition alimentaire anti-cariogène. |
-
1995
- 1995-06-16 DE DE69523294T patent/DE69523294T2/de not_active Expired - Fee Related
- 1995-06-16 PT PT95201618T patent/PT748591E/pt unknown
- 1995-06-16 AT AT95201618T patent/ATE206877T1/de not_active IP Right Cessation
- 1995-06-16 EP EP95201618A patent/EP0748591B1/fr not_active Expired - Lifetime
- 1995-06-16 ES ES95201618T patent/ES2163472T3/es not_active Expired - Lifetime
-
1996
- 1996-06-12 NZ NZ286802A patent/NZ286802A/en unknown
- 1996-06-13 NO NO962497A patent/NO962497L/no not_active Application Discontinuation
- 1996-06-14 AU AU56002/96A patent/AU706125B2/en not_active Ceased
- 1996-06-14 ZA ZA9605102A patent/ZA965102B/xx unknown
- 1996-06-14 FI FI962471A patent/FI962471A/fi unknown
- 1996-06-14 CN CNB961061839A patent/CN1137138C/zh not_active Expired - Fee Related
- 1996-06-14 US US08/665,120 patent/US5833953A/en not_active Expired - Fee Related
- 1996-06-14 JP JP15406296A patent/JP3902264B2/ja not_active Expired - Fee Related
- 1996-06-14 CA CA002178982A patent/CA2178982A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CA2178982A1 (en) | 1996-12-17 |
NZ286802A (en) | 1998-07-28 |
AU5600296A (en) | 1997-01-02 |
NO962497L (no) | 1996-12-17 |
ES2163472T3 (es) | 2002-02-01 |
CN1137138C (zh) | 2004-02-04 |
ZA965102B (en) | 1997-12-15 |
JPH092928A (ja) | 1997-01-07 |
AU706125B2 (en) | 1999-06-10 |
DE69523294D1 (de) | 2001-11-22 |
US5833953A (en) | 1998-11-10 |
ATE206877T1 (de) | 2001-11-15 |
EP0748591A1 (fr) | 1996-12-18 |
FI962471A (fi) | 1996-12-17 |
JP3902264B2 (ja) | 2007-04-04 |
NO962497D0 (no) | 1996-06-13 |
EP0748591B1 (fr) | 2001-10-17 |
PT748591E (pt) | 2002-04-29 |
DE69523294T2 (de) | 2002-04-18 |
FI962471A0 (fi) | 1996-06-14 |
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