CN101600835A - 生物功能材料 - Google Patents

生物功能材料 Download PDF

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CN101600835A
CN101600835A CNA2007800328387A CN200780032838A CN101600835A CN 101600835 A CN101600835 A CN 101600835A CN A2007800328387 A CNA2007800328387 A CN A2007800328387A CN 200780032838 A CN200780032838 A CN 200780032838A CN 101600835 A CN101600835 A CN 101600835A
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protein
digestible protein
substrate
composition
stain
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王平
张敏娟
贾鸿飞
A·H·特里维迪
石井雅彦
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Toyota Motor Corp
University of Akron
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Toyota Motor Engineering and Manufacturing North America Inc
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Abstract

本发明涉及自净系统领域中使用消化蛋白的组合物和方法。一种组合物包括底物，能够分解污迹分子的消化蛋白以及与所述消化蛋白和所述底物结合的连接部分。可选择的组合物包括能够分解污迹分子的消化蛋白和涂敷底物，其中所述的消化蛋白可以被分散于所述涂敷底物中。方法权利要求包括使底物与表面结合并且使消化蛋白与所述底物之间形成连接部分。

Description

生物功能材料
相关申请的交叉参考
本申请请求2006年11月22日提交的美国专利申请顺序号US11/562,503的优先权。
发明背景
1.发明领域
本发明涉及自净组合物和防止和减少因鸟粪，昆虫废物，食物碎屑和其它产生污迹的物质导致的表面污迹蓄积的方法。
2.技术背景
汽车内和外表面，诸如涂层，油漆和座位织物在它们处于长期接触鸟粪，昆虫碎片，松叶树脂，微生物，树胶时发生污染和侵蚀。某些污迹，诸如来源于昆虫的污迹难以通过定期自动无刷洗涤除去。内表面和涂层还可能易于被食物和饮料中的油，蛋白质，糖和其它组分弄脏并且定时除去这类污迹可能存在某些挑战。
在本文中，本发明具体涉及将消化蛋白，包括溶菌酶，蛋白酶，脂酶，纤维素酶等掺到表面，诸如油漆和涂层上。消化蛋白的催化活性使正在进行的自净能够减少和消除污迹污染。这些消化蛋白的作用机制性质上主要是酶促的并且不涉及使用任何腐蚀性或氧化性成分；因此，它们对环境有利。
在这项工作中的初始阶段关注的污迹包括由昆虫破碎体，动物(如鸟)废物，食物，牛奶和其它饮料以及化妆品和个人护理产品形成的污迹。尽管详细成分随污迹来源的不同而改变，但是粘附于表面上的污迹的主要成分为蛋白质，多糖，脂肪或油。
3.相关领域的描述
已知将酶掺入涂层或底物的目的在于给表面提供抗微生物，抗真菌或防污浊特性。就申请人所知使消化蛋白附着于表面以便酶促分解与表面接触的污迹分子是新颖的。
U.S.6,818,212中披露了用于消毒和杀灭微生物细胞的酶促抗微生物组分。
Wang等2001中披露了在潮湿条件下酶在其共价结合时寿命延长；而该参考文献中似乎并未提及在表面自净领域中应用这类共价结合的酶。
U.S.3,705,398中披露了具有活性抗菌，抗真菌和抗菌与抗真菌特性组合的聚合物制品。抗菌和抗真菌活化剂分布在聚合物组合物内并且迁移至表面。
U.S.5,914,367中披露了制备聚合物-蛋白质复合物的方法，包括在溶于有机相中的蛋白质存在下通过蛋白质与表面活性剂的离子配对使单体聚合。然而，该参考文献中似乎并未提及利用这种聚合物-蛋白质复合物的消化能力防止或减少污迹蓄积。
U.S.6,150,146中披露了以受控速率从基质中释放具有抗微生物活性的化合物的方法。该方法预先在基质内包括酶和底物以使该酶和底物彼此在基质中反应，由此产生具有抗微生物活性的化合物。该专利还披露了涂敷组合物，它包含成膜树脂，酶，底物和能够与底物反应的任何酶。
U.S.2005/0058689中披露了具有抗真菌生长和抗菌物质的油漆和涂层。披露了用于掺入涂了漆的表面中的特定化学品和形成物，它们为抑制霉菌，细菌和真菌在建筑材料上生长的抗真菌组合物。
本发明的目的在于提供防止和减少污迹蓄积的含消化蛋白的自净组合物和方法。
发明概述
本发明在第一个方面中提供了包含底物，能够分解污迹分子的消化蛋白和连接部分的组合物。
本发明的组合物可以用作通过“自动”酶促降解反应防止接触污迹和污物蓄积的机制。该组合物中的消化蛋白可以包括水解蛋白分子的蛋白酶，水解脂质和脂肪的脂酶，水解纤维素的纤维素酶和水解碳水化合物的淀粉酶等。对消化蛋白而言既不需要，也无必要使它们具有均面对污迹颗粒的功能性结合袋。尽管消化蛋白可以随机排列在表面上，但是消化蛋白层提供足够的覆盖度和消化活性。
在本发明的一个优选的实施方案中，可以使用包含一个或多个活性基团的聚合物层预处理表面。可以将消化蛋白混悬液旋转涂敷在带有活性基团的聚合物层上以便在蛋白质与聚合物层之间形成共价键。活性基团可以包括醇，硫醇，醛，羧酸，酸酐，环氧化物和酯等。可选择地，可以使消化蛋白在与油漆或涂层混悬前附着于纳米上。
本发明可以进一步涉及：包含用于分解污迹分子的消化蛋白和涂敷底物的组合物，其中消化蛋白被截留在涂敷底物中。在该组合物中，消化蛋白可以选自溶菌酶，蛋白酶，脂酶，纤维素酶，糖苷酶，淀粉酶等。
在本发明的另一个方面中，披露了用于减少和或消除污迹污染的方法。该方法包括使底物与表面结合并且在消化蛋白的活性基团与底物之间形成连接部分。在该方法中，所述的底物可以包含表面官能团，诸如醇，硫醇，醛，羧酸，酸酐，环氧化物，酯或其任意的组合。
附图简述
通过参照附图进一步例证本发明，其中
图1为使酶与聚合物纳米颗粒表面附着的描述。
图2为通过吸附和共价交联制备的蛋白酶涂层的荧光影像描述。
图3表示蛋白质测定校准曲线。
图4表示用于酪氨酸(水解产物)的校准曲线。
图5表示显示卵清污迹降解的有代表性的GPC色谱图。
图6表示卵清污迹降解的时程。
图7表示在80℃下蛋白酶涂层的热稳定性。
发明详述
本发明在第一个方面涉及包含底物，能够分解污迹分子的消化蛋白和连接部分的组合物。
本发明具体地涉及将一种或多种消化蛋白掺到诸如油漆和涂层这类表面上，所述的消化蛋白包括溶菌酶，蛋白酶，脂酶，纤维素等。这些消化蛋白的催化活性使正在进行的自净能够减少和消除污迹污染。
各种污迹包括由昆虫破碎体，动物(如鸟)废物，食物，牛奶和其它饮料以及化妆品和个人护理产品形成的污迹。尽管详细成分随污迹来源的不同而改变，但是粘附于表面上的污迹的主要成分为蛋白质，多糖，脂肪或油。
在溶液环境中评价消化蛋白对不同污迹来源的活性。在不同条件下进行试验，包括不同pH和温度，目的在于尝试评价该蛋白质在汽车环境而不是在传统上应用它们的洗涤机中的性能。试验包括蛋白质相关活性；淀粉相关活性试验；使用油污迹的试验。将蛋白质活性单位定义为：在测定条件下于37℃1个单位的消化蛋白水解酪蛋白而产生相当于1.0μmol酪氨酸/分钟的吸收度差异。活性测定的结果表明共价交联的蛋白酶呈现的活性比物理吸附的蛋白酶的活性高9倍。
存在几种将消化蛋白掺到底物上的方式。其中之一涉及应用共价键。具体地，消化蛋白的游离胺基可以与底物的活性基团共价结合。这类活性基团包括醇，硫醇，醛，羧酸，酸酐，环氧化物，酯或其任意的组合。这种掺入消化蛋白的方法提供独特的优点。首先，该共价键束缚了与底物持久结合的蛋白质且由此使它们成为消化蛋白种类渗漏程度极低(即使并非全部)的最终组合物的组成部分。其次，该共价键提供了延长的酶寿命。随着时间的推移，蛋白质一般因其多肽链解折叠而失去活性。诸如共价键合这类化学结合有效地限制这样的解折叠，且由此改善蛋白质的寿命。蛋白质的寿命一般通过比较一段时间内游离的或物理吸附的蛋白质活性降低的量与共价固定的蛋白质活性降低的量来确定。结果已经证实游离形式的或物理吸附于底物上的蛋白质失去其活性远快于共价键形式的蛋白质。
可选择地，消化蛋白可以均匀地分散于整个底物网状结构中以生成均匀的蛋白质平台。在如此进行的过程中，消化蛋白可以首先被可聚合基团修饰。修饰的蛋白质可以在有表面活性剂存在下增溶于有机溶剂中，且由此能够随后与有机溶液中诸如甲基丙烯酸甲酯(MMA)或苯乙烯这类单体聚合。所得组合物包括均匀分散于整个网状结构中的消化蛋白分子。
此外，与上述交联方法相比，消化蛋白可以附着于底物表面上。使用具有100-1000nm直径的聚苯乙烯颗粒实现了相当于～100％表面覆盖度的消化蛋白附着。
组合物的消化蛋白可以包括水解蛋白质分子的蛋白酶，水解脂质和脂肪的脂酶，水解纤维素的纤维素酶和水解碳水化合物的淀粉酶。对消化蛋白而言既不需要也无必要使它们具有均面对污迹颗粒的功能性结合袋。尽管消化蛋白可以随机排列在表面上，但是消化蛋白层提供足够的覆盖和消化活性。
在本发明的一个优选的实施方案中，用包含一个或多个琥珀酰亚胺酯的表面活性基团的聚合物层预处理表面。将消化蛋白的混悬液旋转涂敷于具有活性基团的聚合物层上，以便与蛋白质形成共价键。可选择地，消化蛋白可以在与油漆或涂层混悬前附着于纳米颗粒上。
本发明进一步涉及包括能够分解污迹分子的消化蛋白和涂敷底物的组合物，其中消化蛋白可以被截留在涂敷底物内。在该组合物中，所述的消化蛋白可以选自溶菌酶，蛋白酶，脂酶，纤维素酶，糖苷酶和淀粉酶。
在本发明的另一个方面中，披露了减少和或消除污迹污染的方法。该方法包括使底物与表面结合并且在消化蛋白的活性基团与底物之间形成连接部分。在该方法中，所述的底物可以包含表面活性基团，诸如醇，硫醇，醛，羧酸，酸酐，环氧化物，酯或其任意的组合。
实施例1
可以使酶附着在塑料表面上。可以使用具有100-1000nm直径的聚苯乙烯颗粒实现相当于～100％表面覆盖的酶附着。通过用消化蛋白涂敷，可以将这些颗粒与油漆或涂层一起使用以便使物质表面官能化。相同的化学手段可以应用于涂敷在塑料部分上施加的酶，且由此在该部分的表面上形成蛋白质涂层。正如图1中所示，可以通过乳液聚合合成具有100-1000nm直径的颗粒。乳液聚合为一般掺入水，单体和表面活性剂的乳液中进行的聚合类型。最常用乳液聚合类型为水包油型乳液，其中单体(油)液滴在水的连续相中被乳化(使用表面活性剂)。
可以通过混合含可聚合表面活性剂(2-磺基乙基甲基丙烯酸酯)，稳定剂(聚乙烯吡咯烷酮，PVP)和引发剂(2，2′-偶氮双[2-甲基-N-(2-羟乙基)丙酰胺]的水溶液(水和乙醇的混合物，～20ml)合成如上所述的颗粒，使其与苯乙烯，N-丙烯酰氧基琥珀酰亚胺(NAS，官能化乙烯基单体)，和乙烯基苯(～1％v/v)的有机溶液(～1ml)混合。可以通过调整相比(1/30-1/15，油/水)和乙醇浓度(0.125-0.50ml/ml)，甲基丙烯酸2-磺基乙基酯和PVP(0-5.5mg/ml)来控制粒度。可以在70℃下通过搅拌10h进行反应，随后用乙醇和DI水在带有聚醚砜膜(MW截止值：300kDa)的搅拌超滤池内洗涤所得颗粒。
实施例2
污迹可以由不同的接触来源生成。昆虫残体，动物废物，食物，牛奶和其它饮料以及化妆品和个人护理产品均可以产生污迹。尽管详细成分随污迹来源的不同而改变，但是粘附于表面的主要成分为蛋白质，简单糖类和多糖类，脂肪和/或油。消化蛋白，包括脂酶，蛋白酶，淀粉酶和纤维素酶各自攻击不同的成分，它们迄今为止为最有效，安全和经济的对抗这类污迹的试剂。正如表1中所示，在我们的初步筛选试验中检验和测试这些蛋白质，且最终我们因活性测定的便利性而选择了蛋白酶进行随后的大部分实验。
表1
  酶   靶向污迹   来源   功能   标准测试条件
  蛋白酶   昆虫，奶制品，动物废物   地衣形芽孢杆菌(Bacilluslicheniformis)(SubtilisinCarlsberg)   水解蛋白质物质   使用Folin &Ciocalteu′s酚染料，pH7.5，37℃，在660nm处的吸收度
  脂酶AK   脂肪和油，化妆品，墨水   荧光假单胞菌(Pseudomonasfluorescens)   水解油和脂肪   对硝基苯基戊酸酯，pH 7.7，40℃，在405nm处的吸收度
  α-淀粉酶   果汁，软饮料，食物，动物废物   枯草芽孢杆菌(Bacillussubtilis)   水解淀粉   染色淀粉，pH6.9，25℃，在540nm处的吸收度
  纤维素酶   饮料，食物，动物废物   黑曲霉(Aspergillusniger)   水解纤维素   染色纤维素，pH 6，50℃，在590nm处的吸收度
实施例3
酶涂层的制备
将N-丙烯酰氧基琥珀酰亚胺(392mg)，1.2ml苯乙烯和29.2mg4，4’-偶氮双-(4-氰基戊酸)与16ml氯仿在20ml玻璃反应瓶中混合。给该瓶充氮气，密封并且在70℃和搅拌下温育12小时，随后通过充氮气除去溶剂。将聚合物产物以50mg/ml的浓度再溶于氯仿。将1毫升所得溶液以6000rpm旋转涂敷在聚苯乙烯平板(直径11cm)上。将来自Subtilisin Carlsberg的蛋白酶以10mg/ml的浓度溶于0.05M磷酸盐缓冲液。将酶通过3-步叠层旋转涂敷涂布在活性聚合物涂敷的平板上：1)1ml蛋白酶溶液，2)含0.5％(V/V)戊二醛的1ml蛋白酶溶液，3)1ml蛋白酶溶液。将旋转涂敷的平板保持在4℃下12小时，随后用0.05M Tris缓冲液(pH 8)，2M NaCl溶液和DI水强洗涤。最终使平板风干并且切成小片(1×2cm)。将该方法命名为共价交联。作为对比，将类似的程序应用于不含活性聚合物涂层的聚苯乙烯平板，这称作物理吸附。
实施例4
酶涂层的显影
首先将荧光染料(Oregon green，Invitrogen Corp.)以2mg/ml的浓度溶于二甲亚砜。在室温与适度振摇下将具有物理吸附和共价固定酶的样品平板在所述染料溶液中温育2小时，随后用DI水冲洗。然后在氮气中干燥平板并且在荧光显微镜下观察。影像如图2中所示，其中绿色表示该区域被酶覆盖。与物理吸附相比，使用共价交联法使更多的酶被固定在表面上。
实施例5
酶荷载的测定
通过逆向Bradford法测定附着在塑料平板上的酶的量。一般而言，首先通过用DI水(1∶5，按体积计)稀释Bradford试剂制备操作溶液。首先使用游离蛋白酶作为标准品获得校准曲线。在1ml比色杯中，将0.5ml蛋白酶溶液与0.5ml操作溶液混合且然后使其反应5分钟。使用分光光度计在465nm处测定该溶液的吸收度。在测试一系列不同蛋白酶浓度后，获得如图3中所示的校准曲线。
为了测定固定酶的载荷，将一块酶涂敷的平板(1cm×2cm)放入20-ml玻璃瓶中，随后添加0.5ml DI水和0.5ml操作溶液。在室温下将该瓶适度搅拌5分钟以便使染料与固定酶结合。然后在465nm处记录上清液的吸收度。类似地还将不含酶涂敷的空白塑料平板测定为对照。从获自酶荷载平板的读数中扣除使用空白平板获得的读数。将获得的读数差异与校准曲线比较得到该平板上的载荷，然后将其标准化成μg/cm2。通过共价交联和物理吸附得到的酶载荷分别为8.5和1.0μg/cm2。
实施例6
酶涂层的水解活性的验证：
在溶液中的酶：使用0.65％(w/v)酪蛋白作为底物测定蛋白酶的蛋白水解活性。将蛋白酶溶液(0.1ml)与0.5ml酪蛋白溶液一起在37℃下温育10分钟。通过添加0.5ml三氯乙酸(110mM)终止反应。将该混合物离心以便除去沉淀。将所得上清液(0.4ml)与1ml碳酸钠(0.5M)和0.2ml稀Folin & Ciocalteu′s酚试剂(通过用DI水按照1∶4稀释Folin & Ciocalteu′s酚试剂)混合，随后在37℃下温育30分钟。最终再次离心该混合物并且使用分光光度计在660nm处测定上清液的吸收度。通过添加100μl缓冲液并且进行类似试验进行不使用酶溶液的空白实验。从样品(酶溶液)中扣除空白的吸收度。
将活性单位定义为：1个单位的酶在37℃和测定条件下酶水解酪蛋白产生与1.0μmol酪氨酸/分钟相当的吸收度差异。酪氨酸氨基酸用于校准。使不同浓度的酪氨酸与Folin-Ciocalteau试剂反应并且所得校准曲线如图4中所示。
酶涂层：通过使用酶涂敷的聚合物片(1×2cm)而不是在溶液中的酶和空白聚合物涂敷的片作为对照，按照类似方式测定固定蛋白酶的活性。将蛋白质的活性称作每单位面积的表面活性。
活性测定结果表明具有共价交联的蛋白酶的平板得到5.6×10-3个单位/cm2，而物理吸附的每仅展示出0.6×10-3个单位/cm2的活性。
实施例7
酶涂层上的污迹降解
将卵清作测定酶涂层上污迹降解的模型污迹。在具有蛋白酶涂敷的平板(11cm直径)上，以2000rpm旋转涂敷(在DI水中10mg/ml)2ml卵清溶液。然后将平板切除较小块(1×2cm)并且保持在室温下(25℃)不同时间期限，以使卵清降解。在一定间隔后，谨慎地用DI水洗涤1小块平板并且使用凝胶渗透色谱法(GPC)分析洗涤溶液中的卵清，以便测定分子量改变。一般在GPC色谱仪中发现两个峰(图5)：一个具有较短的保留时间，而另一个具有较长的保留时间，分别相当于卵清和降解产物。基于卵清峰的面积，获得如图6中所示的蛋白降解时程。还使用不含蛋白酶涂敷的平板进行对照实验，但未鉴定出清楚的产物峰。
实施例8
酶涂层的热稳定性
在80℃下的空气加热箱内研究酶涂层的热稳定性。在一定时间间隔，从箱内取出样品平板并且按照如操作实施例2中所示的程序测定活性。将活性降低与时间的关系绘制在图9中。与物理吸附的酶相比，显然共价交联酶得到了对热失活的较好稳定性。本发明并不限于上述例证性实施例。
这些实施例并不作为对本发明范围的限定。本文所述的方法，仪器和组合物等为典型的，但不作为对本发明范围的限定。本文的改变和其它应用对本领域技术人员而言是显而易见的。本发明的范围由权利要求的范围确定。

Claims (17)

1.组合物，包含：
能够分解污迹分子的消化蛋白；
底物；和
与所述底物和所述消化蛋白的活性基团结合的连接部分。
2.权利要求1所述的组合物，其中所述的消化蛋白包括溶菌酶，蛋白酶，脂酶，纤维素酶，糖苷酶，淀粉酶。
3.权利要求1所述的组合物，其中所述的污迹分子选自蛋白质，油，脂肪，碳水化合物和纤维素。
4.权利要求1所述的组合物，其中所述的底物包括一个或多个选自醇，硫醇，醛，羧酸，酸酐，环氧化物和酯的基团。
5.权利要求1所述的组合物，其中所述的活性基团选自醇，胺，硫醇和羧酸。
6.权利要求1所述的组合物，其中所述的连接部分为共价键。
7.权利要求1所述的组合物，其中被所述消化蛋白分解的所述污迹分子的终产物是可通过水冲洗除去的。
8.组合物，包含：
能够分解污迹分子的消化蛋白；
涂敷底物，其中所述的消化蛋白被截留在所述涂敷底物中。
9.权利要求8所述的组合物，其中所述的消化蛋白包括溶菌酶，蛋白酶，脂酶，纤维素酶，糖苷酶，淀粉酶。
10.权利要求8所述的组合物，其中所述的污迹分子选自蛋白质，油，脂肪，碳水化合物和纤维素。
11.权利要求8所述的组合物，其中所述的涂敷底物包括油漆，聚合物和其它涂层。
12.自净方法，包括：
使底物与表面结合；和
使消化蛋白的活性基团与所述底物之间形成连接部分。
13.权利要求12所述的方法，其中所述的底物包括一种或多种选自醇，硫醇，醛，羧酸，酸酐，环氧化物和酯的基团。
14.权利要求12所述的方法，其中所述的表面选自金属，玻璃，漆，塑料和织物。
15.权利要求12所述的方法，其中所述的活性基团选自醇，胺，硫醇和羧酸。
16.权利要求12所述的方法，其中所述消化蛋白对污迹分子的降解发生在干燥环境中。
17.权利要求16所述的方法，其中所述降解的终产物是可被水或雨水除去的。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113473856A (zh) * 2019-03-06 2021-10-01 居里公司 防腐剂组合物及其使用方法
CN114395918A (zh) * 2021-12-29 2022-04-26 江苏恒生环保科技有限公司 一种能根治及预防螨虫危害的床品面料的制备方法

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040109853A1 (en) 2002-09-09 2004-06-10 Reactive Surfaces, Ltd. Biological active coating components, coatings, and coated surfaces
US20090238811A1 (en) * 2002-09-09 2009-09-24 Mcdaniel C Steven Enzymatic Antimicrobial and Antifouling Coatings and Polymeric Materials
US8618066B1 (en) 2003-07-03 2013-12-31 Reactive Surfaces, Ltd., Llp Coating compositions having peptidic antimicrobial additives and antimicrobial additives of other configurations
US9828597B2 (en) 2006-11-22 2017-11-28 Toyota Motor Engineering & Manufacturing North America, Inc. Biofunctional materials
GB0808350D0 (en) * 2008-05-09 2008-06-18 Airbus Uk Ltd Self-cleaning surfaces
GB0901966D0 (en) * 2009-02-05 2009-03-11 Danisco Composition
WO2011034931A2 (en) * 2009-09-15 2011-03-24 Reactive Surface, Ltd. Anti-fouling paints and coatings
US8932717B2 (en) 2009-09-18 2015-01-13 Lg Chem, Ltd. Lipolytic enzyme for formation of anti-fingerprint coating, method of forming anti-fingerprint coating, substrate comprising the anti-fingerprint coating formed by the method, and product comprising the substrate
US9121016B2 (en) 2011-09-09 2015-09-01 Toyota Motor Engineering & Manufacturing North America, Inc. Coatings containing polymer modified enzyme for stable self-cleaning of organic stains
US11015149B2 (en) * 2010-06-21 2021-05-25 Toyota Motor Corporation Methods of facilitating removal of a fingerprint
US9388370B2 (en) * 2010-06-21 2016-07-12 Toyota Motor Engineering & Manufacturing North America, Inc. Thermolysin-like protease for cleaning insect body stains
US8796009B2 (en) * 2010-06-21 2014-08-05 Toyota Motor Engineering & Manufacturing North America, Inc. Clearcoat containing thermolysin-like protease from Bacillus stearothermophilus for cleaning of insect body stains
US8394618B2 (en) 2010-06-21 2013-03-12 Toyota Motor Engineering & Manufacturing North America, Inc. Lipase-containing polymeric coatings for the facilitated removal of fingerprints
US10988714B2 (en) * 2010-06-21 2021-04-27 Regents Of The University Of Minnesota Methods of facilitating removal of a fingerprint from a substrate or a coating
US8911986B2 (en) * 2011-04-29 2014-12-16 Toyota Motor Engineering & Manufacturing North America, Inc. Coatings containing polymer modified enzyme for stable self-cleaning of organic stains
DE102012110664A1 (de) * 2012-11-07 2014-05-08 Henkel Ag & Co. Kgaa In Beschichtungsmitteln, Haftvermittlern oder Klebstoffen für oxidische Oberflächen einsetzbare Peptide
CN111175220A (zh) * 2020-02-24 2020-05-19 中国第一汽车股份有限公司 一种人工鸟粪液以及涂层耐鸟粪性能的检测方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998200A (en) * 1985-06-14 1999-12-07 Duke University Anti-fouling methods using enzyme coatings
US6291582B1 (en) * 1996-10-10 2001-09-18 Biotechnology Research & Development Corp. Polymer-protein composites and methods for their preparation and use

Family Cites Families (189)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3220928A (en) * 1962-07-06 1965-11-30 Schwarz Lab Inc Enzymatic cleaning process
US3519538A (en) 1968-09-05 1970-07-07 Corning Glass Works Chemically coupled enzymes
US3672955A (en) 1970-05-20 1972-06-27 Us Agriculture Preparation of an insoluble active enzyme
US3705938A (en) * 1971-02-02 1972-12-12 Hercules Protective Fabric Cor Activated polymer materials and process for making same
US3857934A (en) * 1971-02-02 1974-12-31 Herculite Protective Fab Activated polymer materials and process for making same
US4034078A (en) 1971-02-16 1977-07-05 Ralston Purina Company Product and method for controlling odors
US3935862A (en) 1974-06-12 1976-02-03 Personal Products Company Inhibition of conditions arising from microbial production of ammonia
US4026814A (en) 1974-09-09 1977-05-31 Lever Brothers Company Oxido-reductase in soap
US3957974A (en) 1974-11-05 1976-05-18 Seikenkai Method for deodorization of excrements
DE2625471A1 (de) 1975-06-10 1976-12-23 Grace W R & Co Polyurethanschaum mit in ihm gebundenem biologischen material und verfahren zu seiner herstellung
US4195127A (en) * 1975-06-10 1980-03-25 W. R. Grace & Co. Process for immobilizing proteins
US4016043A (en) * 1975-09-04 1977-04-05 Akzona Incorporated Enzymatic immunological method for the determination of antigens and antibodies
US4195129A (en) * 1975-11-26 1980-03-25 Kansai Paint Co., Ltd. Method for immobilizing enzymes and microbial cells
GB1553633A (en) 1976-02-03 1979-09-26 Nicholas Pty Ltd Management of incontinence
US4098645A (en) * 1976-02-24 1978-07-04 W. R. Grace & Co. Immobilization of proteins with polyurethane polymers
US4195128A (en) 1976-05-03 1980-03-25 Bayer Aktiengesellschaft Polymeric carrier bound ligands
US4094744A (en) * 1976-11-18 1978-06-13 W. R. Grace & Co. Water-dispersible protein/polyurethane reaction product
US4322308A (en) 1977-02-15 1982-03-30 Lever Brothers Company Detergent product containing deodorant compositions
FR2384010A1 (fr) * 1977-03-15 1978-10-13 Nal Pour Expl Oceans Centre Peinture antisalissure
US4237591A (en) 1977-05-23 1980-12-09 Personal Products Company Deodorant mini-pad sanitary napkin
US4315828A (en) 1978-03-10 1982-02-16 Max L. Wymore Water based window glass and chrome cleaner composition
US4229536A (en) 1978-12-28 1980-10-21 Uop Inc. Process for preparing immobilized enzymes
SE432194B (sv) 1980-09-17 1984-03-26 Landstingens Inkopscentral Fukthemmande och bakteriedodande absorptionskropp for urin och faeces, vilken innehaller ett vattenlosligt kopparsalt
US4552813A (en) * 1982-02-12 1985-11-12 Grams Ralph R Method of inhibiting the growth of marine life on surfaces in contact with seawater
FR2539418A1 (fr) 1983-01-13 1984-07-20 Inst Textile De France Nouveaux derives du mercurobutol et leur application a la protection de supports notamment textiles
US4539982A (en) 1983-02-28 1985-09-10 Bailly Richard Louis Odor absorbing wrap
US4551187A (en) 1984-06-08 1985-11-05 Brush Wellman Inc. Copper alloy
JPS6377998A (ja) * 1986-09-19 1988-04-08 日立化成工業株式会社 洗浄剤組成物
JPS6377999A (ja) * 1986-09-19 1988-04-08 日立化成工業株式会社 酵素結合ビルダ−
JP2573936B2 (ja) * 1987-01-06 1997-01-22 株式会社資生堂 改質固体材料
JPS63202677A (ja) 1987-02-19 1988-08-22 Mitsubishi Yuka Badische Co Ltd 防藻用塗料組成物
NO170424C (no) * 1987-03-12 1992-10-14 Nippon Paint Co Ltd Harpikspartikler av desintegrasjonstypen, deres fremstilling og beleggsmiddel inneholdende slike partikler
JPH0693910B2 (ja) 1987-04-23 1994-11-24 日本ゼオン株式会社 脱臭剤入りウレタンフオ−ム及びその製造方法
DK687387D0 (da) 1987-12-28 1987-12-28 Novo Industri As Immobiliseret lipase
US4897352A (en) 1988-01-15 1990-01-30 The Dow Chemical Company Acrylate based adsorbent resin for the immobilization of enzymes
JPH01285188A (ja) * 1988-05-12 1989-11-16 S T Chem Co Ltd リパーゼ固定ポリアクリル酸系材料およびその利用
JPH0268117A (ja) 1988-09-02 1990-03-07 Asahi Chem Ind Co Ltd 消臭エアーフィルター
JP2805799B2 (ja) * 1989-02-28 1998-09-30 大日本インキ化学工業株式会社 固定化された酵素を含有する防汚塗料用複合樹脂およびこれを含む防汚塗料
US5213791A (en) 1989-10-10 1993-05-25 The Gillette Company Amino acid β-lyase enzyme inhibitors as deodorants
EP0521871A4 (en) 1990-02-12 1993-03-10 The Gillette Company Alternative enzyme substrates as deodorants
FR2661682B1 (fr) 1990-05-04 1993-12-10 Norsolor Nouvelles compositions resineuses a base de resines polyesters non saturees et de nouveaux additifs anti-retrait.
CA2051171A1 (en) * 1990-09-14 1992-03-15 Eugene A. Mizusawa Lipase-surface complex and methods of formation and use
US5492821A (en) 1990-11-14 1996-02-20 Cargill, Inc. Stabilized polyacrylic saccharide protein conjugates
KR930002966B1 (ko) * 1990-11-24 1993-04-16 주식회사 미 원 디펩티드의 제조방법
US5559163A (en) * 1991-01-28 1996-09-24 The Sherwin-Williams Company UV curable coatings having improved weatherability
US5279955A (en) 1991-03-01 1994-01-18 Pegg Randall K Heterofunctional crosslinking agent for immobilizing reagents on plastic substrates
US5643559A (en) 1991-10-30 1997-07-01 Colgate-Palmolive Company Deodorant compositions comprising inhibitors of odor-producing axillary bacterial exoenzymes
US5303290A (en) 1991-11-29 1994-04-12 At&T Bell Laboratories System for elminating glare in virtual private line circuits
CA2064683A1 (en) 1992-03-26 1993-09-27 Krishna Mohan Rao Kallury Formation of thermostable enzymes with extra-ordinary heat tolerance by immobilization on phospholipid matrices
US5496710A (en) 1992-06-08 1996-03-05 Sagami Chemical Research Center Protease
JPH08126489A (ja) * 1992-06-24 1996-05-21 Osaka Prefecture 酵素担持基材、酵素担持体及びこれらの製造方法
GB9225054D0 (en) 1992-11-30 1993-01-20 Baxenden Chem Enzymatic synthesis
US5360847A (en) 1993-01-19 1994-11-01 National Starch And Chemical Investment Holding Corp. Dissipative curing and coating composition for concrete
JPH06240297A (ja) * 1993-02-16 1994-08-30 Toray Ind Inc 酵素固定化洗浄用助剤
DE69330340T2 (de) 1993-03-17 2002-05-29 Sagami Chemical Res Ct Sagamih Mutanten von einer thermostabilen neutralen Protease aus Bacillus
GB9309243D0 (en) 1993-05-05 1993-06-16 Allied Colloids Ltd Enzyme dispersions,their production and compositions containing them
US5523226A (en) 1993-05-14 1996-06-04 Biotechnology Research And Development Corp. Transgenic swine compositions and methods
US5739004A (en) 1993-05-20 1998-04-14 Minnesota Mining And Manufacturing Company Biological sterilization indication for use with or without test pack materials or devices
TW306932B (zh) 1993-08-27 1997-06-01 Holland Sweetener Co
JP3366697B2 (ja) 1993-08-27 2003-01-14 オリヱント化学工業株式会社 長波長紫外線吸収剤およびその製造方法
US5800804A (en) 1993-09-09 1998-09-01 The Gillette Company O-acyl serines and threonines as deodorants
JP2678341B2 (ja) 1993-09-27 1997-11-17 富士紡績株式会社 固定化リパーゼ
EP0728196B1 (en) 1993-12-07 2003-05-02 Sagami Chemical Research Center Mutants of a thermostable neutral protease from bacillus
TW287192B (zh) 1994-01-21 1996-10-01 Ei Du Pont De Nemours Amd Co
DE4406753A1 (de) 1994-03-02 1995-09-07 Basf Lacke & Farben Reinigungsmittel, Verfahren zur Herstellung des Reinigungsmittels sowie seine Verwendung
US5505713A (en) 1994-04-01 1996-04-09 Minimed Inc. Indwelling catheter with stable enzyme coating
US5593398A (en) 1994-05-25 1997-01-14 Weimer; Chester L. Protective underwear with malodorous flatus filter
DE4439669A1 (de) 1994-11-07 1996-05-09 Basf Lacke & Farben Wäßriges Zweikomponenten-Polyurethan-Beschichtungsmittel, Verfahren zu seiner Herstellung und seine Verwendung in Verfahren zur Herstellung einer Mehrschichtlackierung
US5543309A (en) 1994-11-28 1996-08-06 Pischel; Ernie Carrier containing enzymes for treating sewage sludge
US5719039A (en) 1995-06-01 1998-02-17 University Of Iowa Research Foundation Enzyme-surfactant ion-pair complex catalyzed reactions in organic solvents
US5912408A (en) * 1995-06-20 1999-06-15 The Procter & Gamble Company Dry cleaning with enzymes
JP3562668B2 (ja) 1995-07-31 2004-09-08 高砂香料工業株式会社 消臭剤組成物
JPH0959470A (ja) 1995-08-29 1997-03-04 Asahi Chem Ind Co Ltd 水性架橋性樹脂組成物
GB2306473B (en) * 1995-10-26 1998-12-23 Nippon Paint Co Ltd Glucoxide derivatives for enzyme modification, lipid-coated enzymes, method of producing such enzymes and antifouling paint composition
EP0896056A4 (en) 1995-12-11 2001-08-29 Sagami Chem Res NOVEL THERMOLYSIN-LIKE PROTEASE AND USE THEREOF
EP0874893A2 (en) * 1995-12-29 1998-11-04 The Procter & Gamble Company Detergent compositions comprising immobilized enzymes
DE19634122A1 (de) 1996-08-23 1998-02-26 Inst Physikalische Hochtech Ev Neuartige Bäder zur Erzeugung von Mikrostrukturen
AU724492B2 (en) * 1996-10-10 2000-09-21 Biotechnology Research And Development Corporation Polymer-protein composites and methods for their preparation and use
US5837483A (en) 1996-10-15 1998-11-17 Holland Sweetener Company V.O.F. Enzymatic method for producing N-formyl-α-L-aspartyl-L-phenylalanine methyl ester
US6342386B1 (en) * 1996-10-29 2002-01-29 Warren Paul Powers Methods for removing undesired growth from a surface
US5919689A (en) 1996-10-29 1999-07-06 Selvig; Thomas Allan Marine antifouling methods and compositions
JPH10259326A (ja) * 1997-03-17 1998-09-29 Nippon Paint Co Ltd 抗生物活性を有する化合物を徐放する方法、及び、塗料組成物
US5981743A (en) 1997-03-28 1999-11-09 University Of Massachusetts Cyclic ester ring-opened oligomers and methods of preparation
US5817300A (en) 1997-06-02 1998-10-06 Calwood Chemical Industries, Inc. Odor reducing compositions
US6080391A (en) 1997-08-14 2000-06-27 Novo Nordisk A/S Reduction of malodour
BR9811156A (pt) * 1997-08-14 2000-07-25 Novo Nordisk As Composição enzimática antimicrobiana, uso da mesma, e, processos de inibição de microorganismos presentes em roupa suja, de conservação de um produto cosmético, e de limpeza, desinfecção ou inibição de crescimento microbiano em uma superfìcie dura
US5988200A (en) 1997-09-16 1999-11-23 Custom Metalcraft, Inc. Repetitive stamped valve guard
USH1818H (en) * 1997-10-17 1999-11-02 Sasol Technology (Proprietary) Limited Detergent and cleaning compositions derived from new detergent alcohols
US6149636A (en) 1998-06-29 2000-11-21 The Procter & Gamble Company Disposable article having proactive sensors
US6060043A (en) 1998-02-03 2000-05-09 The Gillette Company Deodorant composition containing D-amino acid
AU7275698A (en) 1998-05-01 1999-11-23 Procter & Gamble Company, The Laundry detergent and/or fabric care compositions comprising a modified antimicrobial protein
US6638526B1 (en) 1998-06-23 2003-10-28 Novozymes A/S Polypeptides conjugated to copolymers of ethylene oxide and propylene oxide to reduce allergenicity
US6093869A (en) 1998-06-29 2000-07-25 The Procter & Gamble Company Disposable article having a responsive system including a feedback control loop
US5998512A (en) 1998-07-20 1999-12-07 The University Of Akron Reduced-lipid natural rubber latex
CN1196502C (zh) 1998-07-24 2005-04-13 花王株式会社 除臭吸收性片材
KR20010079898A (ko) * 1998-09-22 2001-08-22 데이비드 엠 모이어 수불용성 기재에 매달린 활성 단백질을 함유하는 신체케어 조성물
US6716610B2 (en) 1998-12-07 2004-04-06 Kao Corporation Esterification or hydrolysis with substrate treated un-dried immobilized lipolytic enzyme
KR20020021395A (ko) * 1999-07-22 2002-03-20 데이비드 엠 모이어 입체적으로 보호된 ｃｌｉｐ 부위를 갖는 프로테아제콘쥬게이트
US6759220B1 (en) 1999-11-17 2004-07-06 Agentase, Llc Enzyme-containing polyurethanes
US6472493B1 (en) 1999-11-23 2002-10-29 E. I. Du Pont De Nemours And Company Clear coating composition having improved early hardness and water resistance
ES2162593B1 (es) 2000-01-20 2002-07-01 Univ Madrid Complutense Procedimiento enzimatico para fluidificar o desprender biofilms de distintas interfases.
WO2001072911A1 (en) * 2000-03-24 2001-10-04 Biolocus Aps Antifouling paint composition comprising rosin and enzyme
US20050164902A1 (en) 2003-10-24 2005-07-28 Ecolab Inc. Stable compositions of spores, bacteria, and/or fungi
US20050272141A1 (en) 2000-08-22 2005-12-08 Ian Crawford Anti-graffiti paint formulations and removal
US6303290B1 (en) 2000-09-13 2001-10-16 The Trustees Of The University Of Pennsylvania Encapsulation of biomaterials in porous glass-like matrices prepared via an aqueous colloidal sol-gel process
AU1142001A (en) * 2000-10-19 2002-04-29 Dsm N.V. Protein hydrolysates
WO2003053325A2 (en) * 2000-12-13 2003-07-03 Purdue Research Foundation Microencapsulation of drugs by solvent exchange
WO2002064877A2 (en) 2001-01-30 2002-08-22 The Procter & Gamble Company Coating compositions for modifying surfaces
JP2002332739A (ja) 2001-05-10 2002-11-22 Oomi Kagaku Touki Kk 外装建材、その製造方法及び外装建材施工方法
US6844028B2 (en) 2001-06-26 2005-01-18 Accelr8 Technology Corporation Functional surface coating
US7335400B2 (en) * 2001-07-24 2008-02-26 University Of Pittsburgh Irreversible immobilization of enzymes into polyurethane coatings
CA2454826A1 (en) * 2001-07-24 2003-08-14 University Of Pittsburgh Irreversible immobilization of diisopropylfluorophosphatase into polyurethane coatings
US7183248B2 (en) 2001-08-23 2007-02-27 Treyco Supply Co. Enzymatic cleaner having high pH stability
US6881711B1 (en) * 2001-10-26 2005-04-19 Prestone Products Corporation Low VOC cleaning compositions for hard surfaces
FR2832145A1 (fr) 2001-11-09 2003-05-16 Atofina Procede de fabrication de monomeres(meth) acryliques porteurs de chaines polylactiques, nouveaux monomeres et leurs applications
JP2003144147A (ja) * 2001-11-15 2003-05-20 Kansai Paint Co Ltd 酵素又は微生物菌体固定化用粒状成形物の製造方法
US7361719B2 (en) 2002-01-31 2008-04-22 Micro Science Tech Co., Ltd. Monomer with anti-microbial character, polymer using the same, and manufacturing method thereof
US20050147579A1 (en) * 2002-04-12 2005-07-07 Biolocus Aps Antifouling composition comprising an enzyme in the absence of its substrate
MY140680A (en) 2002-05-20 2010-01-15 Bristol Myers Squibb Co Hepatitis c virus inhibitors
NZ538146A (en) * 2002-07-12 2006-08-31 Martin J Coatings with at least 2 layers comprising microorganisms that produce amylolytic or proteolytic enzymes enabling enhanced microbial performance
US20110240064A1 (en) * 2002-09-09 2011-10-06 Reactive Surfaces, Ltd. Polymeric Coatings Incorporating Bioactive Enzymes for Cleaning a Surface
US20040109853A1 (en) 2002-09-09 2004-06-10 Reactive Surfaces, Ltd. Biological active coating components, coatings, and coated surfaces
US20120097194A1 (en) * 2002-09-09 2012-04-26 Reactive Surfaces, Ltd. Polymeric Coatings Incorporating Bioactive Enzymes for Catalytic Function
US20110250626A1 (en) * 2002-09-09 2011-10-13 Reactive Surfaces, Ltd. Visual Assays for Coatings Incorporating Bioactive Enzymes for Catalytic Functions
US20100210745A1 (en) 2002-09-09 2010-08-19 Reactive Surfaces, Ltd. Molecular Healing of Polymeric Materials, Coatings, Plastics, Elastomers, Composites, Laminates, Adhesives, and Sealants by Active Enzymes
IL167413A (en) 2002-09-09 2010-12-30 Steven C Mcdaniel Biological active coating components, coatings and coated surfaces
US20090238811A1 (en) * 2002-09-09 2009-09-24 Mcdaniel C Steven Enzymatic Antimicrobial and Antifouling Coatings and Polymeric Materials
US20050058689A1 (en) * 2003-07-03 2005-03-17 Reactive Surfaces, Ltd. Antifungal paints and coatings
US20040063831A1 (en) * 2002-09-30 2004-04-01 Sheppard Aurelia De La Cuesta Polymeric nanoparticle and bioactive coating formulations
US20050079594A1 (en) 2002-10-31 2005-04-14 Karine Marion Method of removing a biofilm
US7691296B2 (en) 2002-11-25 2010-04-06 Amorepacific Corporation Method for stabilizing active components using polyol/polymer microcapsule, and cosmetic composition containing the microcapsule
DE10257094A1 (de) 2002-12-05 2004-06-24 Basf Ag Enzymatische Herstellung urethangruppenhaltiger (Meth)acrylsäureester
JP2004352804A (ja) * 2003-05-28 2004-12-16 Tdk Corp 磁気記録媒体用電子線硬化型樹脂、その製造方法およびそれを用いた磁気記録媒体
US20040242831A1 (en) 2003-05-30 2004-12-02 Dong Tian Enzyme catalyzed polyesters and polyol polymers
EP1639091B1 (en) * 2003-06-17 2012-12-05 California University Of Technology Regio- and enantioselective alkane hydroxylation with modified cytochrome p450
US20040259746A1 (en) * 2003-06-20 2004-12-23 Warren Jonathan N. Concentrate composition and process for removing coatings from surfaces such as paint application equipment
US8618066B1 (en) * 2003-07-03 2013-12-31 Reactive Surfaces, Ltd., Llp Coating compositions having peptidic antimicrobial additives and antimicrobial additives of other configurations
US20050049166A1 (en) * 2003-08-29 2005-03-03 Huang Tsao-Chin Clare Enzyme-based cleaning composition and method of use
EP1660596A1 (en) 2003-09-04 2006-05-31 McDaniel, Steven C. Microorganism coating components, coatings, and coated surfaces
ATE421541T1 (de) 2003-09-11 2009-02-15 Ciba Holding Inc Auf wasser basierende konzentrierte produktformen von lichtschutzmitteln, hergestellt nach einer heterophasen-polymerisationstechnik
JP4939221B2 (ja) 2003-10-10 2012-05-23 ダウ・コーニング・コーポレイション カルビノール官能性シリコーン樹脂を含有するウレタン形成組成物またはウレタン組成物
KR100591282B1 (ko) 2003-11-18 2006-06-19 주식회사 이지싱크 골프 스코어 관리 전용단말기와 이를 이용한 골프 스코어관리 시스템 및 그 관리 방법
WO2005072125A2 (en) 2004-01-16 2005-08-11 Massachusetts Institute Of Technology Composite materials for controlled release of water soluble products
US8216559B2 (en) 2004-04-23 2012-07-10 Jnc Corporation Deodorant fiber and fibrous article and product made thereof
DE102004020355A1 (de) 2004-04-26 2005-11-10 Call, Krimhild Oxidative, reduktive, hydrolytische und andere enzymatische Systeme zur Oxidation, Reduktion, zum Coaten, Koppeln und Crosslinken von natürlichen und künstlichen Faserstoffen, Kunststoffen oder anderen natürlichen und künstlichen Mono- bis Polymerstoffen
US20050277564A1 (en) 2004-06-15 2005-12-15 Heise Karl A Method of formulating a cleaning composition for use in cleaning surfaces
KR100606021B1 (ko) 2004-06-21 2006-07-31 삼성전자주식회사 나노 실버 입자를 함유한 항균 도료 및 그 항균 도료의코팅 방법
WO2006002630A1 (en) * 2004-07-01 2006-01-12 Biolocus A/S Self-polishing anti-fouling coating compositions comprising an enzyme
EP1630163A1 (de) 2004-08-25 2006-03-01 Boehringer Ingelheim Pharma GmbH & Co.KG Dihydropteridinonderivative, Verfahren zu deren Herstellung und deren Verwendung als Arzneimittel
DE602005018081D1 (de) * 2004-10-05 2010-01-14 Siemens Healthcare Diagnostics Stabiler kreatinin-biosensor mit drei enzymen
EP1661955A1 (en) 2004-11-29 2006-05-31 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Antifouling coating comprising a polymer with functional groups bonded to an enzyme
WO2006088248A1 (ja) 2005-02-18 2006-08-24 Nof Corporation ポリオキシアルキレン誘導体
DE102005011719A1 (de) * 2005-03-15 2006-09-28 Clariant Produkte (Deutschland) Gmbh Wasch- und Reinigungsmittel enthaltend Acetale als organische Lösemittel
EP1890761B1 (en) 2005-06-07 2017-08-09 Transfert Plus S.E.C. Methods of increasing lipolysis
EP1919361B1 (en) 2005-08-09 2014-03-12 University of Sunderland Fingerprint analysis using mass spectrometry
AU2006299783B2 (en) 2005-10-12 2012-06-14 Danisco Us Inc. Use and production of storage-stable neutral metalloprotease
US7781388B2 (en) 2006-05-04 2010-08-24 American Sterilizer Company Cleaning compositions for hard to remove organic material
WO2007136645A2 (en) 2006-05-16 2007-11-29 E. I. Du Pont De Nemours And Company Highly productive coating composition for automotive refinishing
EP2032577B1 (en) 2006-06-27 2011-02-02 Basf Se Long wavelength shifted benzotriazole uv-absorbers and their use
GB2456696B (en) 2006-10-23 2012-05-02 Kansai Paint Co Ltd Aqueous two-package type clear coating composition
US9828597B2 (en) * 2006-11-22 2017-11-28 Toyota Motor Engineering & Manufacturing North America, Inc. Biofunctional materials
JP5286677B2 (ja) 2007-03-13 2013-09-11 トヨタ自動車株式会社 Ｐ型４Ｈ−ＳｉＣ基板上のオーミック電極の形成方法
US8222015B2 (en) 2007-05-11 2012-07-17 Toyota Motor Engineering & Manufacturing North America, Inc. Heat resistant bioactive composition
WO2009023171A1 (en) 2007-08-10 2009-02-19 Ethox Chemicals, Llc Styrenated phenol ethoxylates in emulsion polymerization
US20090104086A1 (en) 2007-10-19 2009-04-23 Adam Zax Photocatalytic titanium dioxide nanocrystals
US20110056408A1 (en) * 2007-11-12 2011-03-10 Cismi Aerogel compositions
CN101461719B (zh) 2007-12-18 2012-02-01 深圳迈瑞生物医疗电子股份有限公司 一种多普勒扫描变换实现方法和装置
US8011938B2 (en) 2008-05-21 2011-09-06 Tyco Electroniccs Corporation Electrical connector having linear actuator
EP2324087A4 (en) 2008-05-30 2012-05-30 Mcdaniel Steven C SURFACE COATINGS AND TREATMENTS HAVING ACTIVE ENZYMES AND PEPTIDES
CN102088949B (zh) 2008-06-06 2013-05-01 路博润高级材料公司 用于个人护理产品的酯化合物
US8011381B2 (en) 2008-10-02 2011-09-06 Applied Material, Inc. Balanced purge slit valve
US8388904B1 (en) * 2008-12-22 2013-03-05 Reactive Surfaces, Ltd., Llp Equipment decontamination system and method
US8252571B2 (en) * 2009-05-01 2012-08-28 Toyota Motor Engineering & Manufacturing North America, Inc. Preparation of solvent-borne polymeric bioactive coatings
US8679825B2 (en) * 2009-05-01 2014-03-25 Toyota Motor Engineering & Manufacturing North America, Inc. Method facilitating removal of bioorganic stains from surfaces
US8287658B2 (en) 2009-06-02 2012-10-16 Ecolab Usa Inc. Biodegradable surfactant blend
WO2011034931A2 (en) 2009-09-15 2011-03-24 Reactive Surface, Ltd. Anti-fouling paints and coatings
DE102009029513A1 (de) * 2009-09-16 2011-03-24 Henkel Ag & Co. Kgaa Lagerstabiles flüssiges Wasch- oder Reinigungsmittel enthaltend Proteasen
US8932717B2 (en) 2009-09-18 2015-01-13 Lg Chem, Ltd. Lipolytic enzyme for formation of anti-fingerprint coating, method of forming anti-fingerprint coating, substrate comprising the anti-fingerprint coating formed by the method, and product comprising the substrate
MX2012006616A (es) 2009-12-09 2012-06-21 Procter & Gamble Productos para el cuidado de las telas y el hogar.
US9388370B2 (en) 2010-06-21 2016-07-12 Toyota Motor Engineering & Manufacturing North America, Inc. Thermolysin-like protease for cleaning insect body stains
US9121016B2 (en) * 2011-09-09 2015-09-01 Toyota Motor Engineering & Manufacturing North America, Inc. Coatings containing polymer modified enzyme for stable self-cleaning of organic stains
US8394618B2 (en) 2010-06-21 2013-03-12 Toyota Motor Engineering & Manufacturing North America, Inc. Lipase-containing polymeric coatings for the facilitated removal of fingerprints
US8796009B2 (en) 2010-06-21 2014-08-05 Toyota Motor Engineering & Manufacturing North America, Inc. Clearcoat containing thermolysin-like protease from Bacillus stearothermophilus for cleaning of insect body stains
KR101791599B1 (ko) 2010-10-08 2017-10-30 한국교통대학교산학협력단 벌크 나노 복합체형 열전재료, 나노 복합체형 열전재료 분체 및 그 제조방법
US8324295B2 (en) 2011-02-10 2012-12-04 Toyota Motor Engineering & Manufacturing North America, Inc. UV-stabilized protein-polymer compositions
CN103502418A (zh) 2011-02-16 2014-01-08 诺维信公司 包含金属蛋白酶的去污剂组合物
US8911986B2 (en) 2011-04-29 2014-12-16 Toyota Motor Engineering & Manufacturing North America, Inc. Coatings containing polymer modified enzyme for stable self-cleaning of organic stains
CA2872327A1 (en) 2012-05-21 2013-11-28 Genentech, Inc. Anti-ly6e antibodies and immunoconjugates and methods of use
DE102012112519A1 (de) 2012-12-18 2014-06-18 Eads Deutschland Gmbh Reinigungsgemisch zur Entfernung beziehungsweise Vermeidung von Insektenablagerungen auf Oberflächen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998200A (en) * 1985-06-14 1999-12-07 Duke University Anti-fouling methods using enzyme coatings
US6291582B1 (en) * 1996-10-10 2001-09-18 Biotechnology Research & Development Corp. Polymer-protein composites and methods for their preparation and use

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113473856A (zh) * 2019-03-06 2021-10-01 居里公司 防腐剂组合物及其使用方法
CN113473856B (zh) * 2019-03-06 2024-03-19 居里公司 防腐剂组合物及其使用方法
CN114395918A (zh) * 2021-12-29 2022-04-26 江苏恒生环保科技有限公司 一种能根治及预防螨虫危害的床品面料的制备方法

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