CN1232384A - 作为染料前体的二氨基苯甲酸衍生物 - Google Patents

作为染料前体的二氨基苯甲酸衍生物 Download PDF

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CN1232384A
CN1232384A CN97198601A CN97198601A CN1232384A CN 1232384 A CN1232384 A CN 1232384A CN 97198601 A CN97198601 A CN 97198601A CN 97198601 A CN97198601 A CN 97198601A CN 1232384 A CN1232384 A CN 1232384A
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N·索恩森
O·凯克
R·洛克
T·德斯勒
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Abstract

本发明涉及通式(Ⅰ)的经氧化产生颜色的底物。本发明还涉及所说的底物在角质纤维,特别是头发的染色及纺织品的染色上的用途,染色组合物和染角质纤维的方法。

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作为染料前体的二氨基苯甲酸衍生物
发明领域
本发明涉及二氨基苯甲酸(DABA)在基于过氧化物酶的分析中作为例如邻苯二胺(OPD)的替代物以及在染色组合物中作为染色底物(即染料前体)的用途，以及在对包括纺织品、线和纱的天然或合成纤维进行染色中作为底物的用途。本发明还涉及适合染角质纤维如头发、羊毛、毛皮和皮革等的组合物和染这些角质纤维的方法。
发明背景免疫-化学测定
几种不同的底物已知能用于过氧化物酶联免疫-化学测定，例如ELISA。这些底物经常是有毒的，诱变的或致癌的。
ELISA(酶联免疫吸附测定)是一种测定血清中抗体含量的方法。主要原理是：在大比例稀释的溶液中，许多抗原和塑料表面相结合。因此，如果抗原的大比例稀释溶液在塑料盘中温育一段时间，小孔在缓冲液中洗后，在塑料表面还保留有抗原膜是可能的。如果需要确定诸如血清中的抗体的量，带有其抗原沉积物的盘与血清一起温育，抗体和抗原结合，彻底洗涤后，盘再和标记物温育，如通过共价键连接有一合适酶的抗-免疫球蛋白血清。在该特定的情况下用过氧化物酶。
过氧化物酶-标记复合物和已经有抗体沉积物存在的部位结合。彻底洗涤以去除所有未结合的物质后，一般利用合适的颜色指示剂测定酶活性。酶活性可以通过加入生色底物(产生颜色的化合物)和过氧化氢确定。该酶催化底物还原为有颜色的化合物。产生的吸收度是酶活性的量度。如果血清不含抗体，则将无酶活性；相反，如果存在许多抗体，则酶活性将非常大。可以作出标准曲线，以表明作为抗体浓度函数的酶活性。通过内推法它可以用于估计未知血清样品中抗体的含量。
许多过氧化物酶底物都是芳香胺，包括二氨基联苯胺(DAB),3,3′-二氨基联苯胺四盐酸化物，3,3′,5,5′-四甲基联苯胺(TMD)。另一个不属于芳香胺类的过氧化物酶底物是2,2-连氮基-二(3-乙基-苯并噻唑啉-6-磺酸)(ABTS)，它已被用作确定过氧化物酶制剂的标准，根据Voogd,Van der Stel和Jacobs(1980)，该物质也是诱变剂。
邻苯二胺(OPD)是广泛用于医院和开发实验室的另一种过氧化物酶底物。OPD已知既是诱变的又是致癌的。
进行涉及到使用有毒、诱变或致癌物质的分析的实验人员都处在直接和这些物质接触的极度危险中。为了提供一个安全的工作环境，现在已经作了很大努力以用不太危险的物质代替这些危险物质。染发组合物
除了用作免疫-化学测定的底物外，OPD还用于染发。在这一方面也需要用一种不太危险的物质代替这一危险物质，以便使用者不由于接触它而处在危险中。为了保护手不受危险物质的损害，当用染发剂时一般带手套。当然，手套不能保护被染发者的头皮。
当今市场上的染发组合物通常可分为三类：-暂时染发剂，-半永久染发剂，和-永久氧化染发剂。
暂时染发剂仅短时间地改变头发的自然颜色，通常通过沉积在头发表面上起作用。这种染发剂易被普通香波去除。
当使用半-永久染发剂时，所染发的颜色可耐受五到更多次香波的洗涤。这是通过利用和头发角蛋白有较高亲和力以及能渗入头发鳞片内部的染发剂实现的。
永久染发剂非常耐光照、香波和其它头发处理过程，仅需要当新发长出时每月一次地更新。利用这些染发系统将染色剂直接施于头发上和头发里。小的芳香类无色染料前体(如对苯二胺、邻-氨基苯酚、邻苯二胺(OPD))深深地渗透到头发里，在这里，所说的染料前体被氧化剂氧化成有色的多聚化合物。这些有色的化合物比染料前体大，不能从头发中洗掉。
通过在染发组合物中包含称之为修饰剂(或成色剂)的化合物，可以得到许多头发色彩的染发剂。儿茶酚和间苯二酚是其中的两例。
当今应用最广泛的一些染料前体，如OPD，已知都是既诱变又致癌的。
而且，传统上H2O2用作氧化剂(颜色助剂)，但它也是漂白剂。由于H2O2的这种淡化效应，含有H2O2的染色组合物经常称作“淡化染色剂”。
由于H2O2损伤头发，它在染色组合物中的应用有一些缺点。再者，氧化染色通常需要高的pH(一般在pH9-10左右)，这也使头发和皮肤遭受损伤。因此，如果利用含有H2O2的染色组合物，不提倡经常染发。
为了克服使用H2O2的缺点，有人提出用氧化酶代替H2O2。
美国专利3,251,742(Revlon)描述了一种通过原位(即在头发上)染色的方式染人类头发的方法。一种氧化酶在基本上中性pH(7-8.5)下用于产生颜色的反应。提到漆酶、酪氨酸酶、多酚氧化酶和儿茶酚酶是合适的氧化酶。通过各种产生醌的化合物和在芳香环上具有氨基的含有单或多芳香胺的控制氧化在头发上形成看起来自然的色素。特别提到的染料前体有2-氨基-4-硝基苯酚，对-苯二胺，间-苯二胺，邻-苯二胺，2-氨基-1,4-萘醌，间-氨基苯酚，对-氨基苯酚，邻-氨基苯酚，2-氨基间苯二酚，1,2,4-苯三胺，硝基-对苯二胺，2-氨基-5-二乙基氨基甲苯。
欧洲专利504,005(Perma S.A.)涉及不需要H2O2(过氧化氢)的存在用于角质纤维，特别是头发的染色组合物。该组合物包含在使组合物pH在6.5和8之间的缓冲液中，能催化聚合染料以及染料前体(如碱和成色剂)产生的酶，所说的酶在6.5到9的pH范围内有最适活性。Rhizoctonia praticola漆酶和Rhus vernicifera漆酶是氧化染料前体的氧化酶。特别提到下列染料前体：对-苯二胺，邻-氨基苯酚，对-甲氨基苯酚，对-氨基苯酚，对-甲代苯二胺和N-苯基-对-苯二胺。
本发明的目的是利用本发现以得到一种对于所有的意图和目的都是无毒的、非诱变的和/或非致癌的、且能用于免疫-化学测定中的底物，用于染角质纤维，特别是头发，用于染天然或合成纤维，如纺织物。该目的是通过利用所发现的包含具有Ⅰ中所示的通式的基团的底物达到的：
Figure A9719860100081
其中R是氨基，单或分布的氨基或OR′，其中R’是H，烷基，链烯基，炔基，卤化烷基，硝基，苄基，苯基或取代苯基。X,Y和Z可以分别是下列中的任何一种：烷基，链烯基，炔基，卤化烷基，硝基，苄基，苯基，取代苯基，氨基，羟基或巯基，其前提是X,Y和Z基团中至少有一个是氨基或氨基盐。
在本发明的一个特定的实施方案中，可得到和式Ⅰ有联系的底物，其中R′是甲基，乙基或异丙基。
在一个优选的实施方案中，底物是苯甲酸酯，特别是3,4-二氨基苯甲酸甲酯(DABA-Me),3,4-二氨基苯甲酸乙酯和3,4-二氨基苯甲酸异丙酯。
将毒性很大的苯胺和苯胺的羧酸衍生物对-氨基苯甲酸(PABA)相比表明通过羧基的加入使分子毒性发生实质性改变。通常认为PABA是无毒的，在其它的应用中，它被用作防晒液中的紫外过滤剂。如果在同一水平上考虑底物OPD，可以发现可能的类似物是3,4-二氨基苯甲酸(3,4-DABA)。该物质相对来说便宜，而且容易得到。
Figure A9719860100091
利用该酶的研究表明3,4-DABA对过氧化物酶来说是比OPD弱的底物。也就是说，3,4-DABA和OPD相比在相同的V最大下有较高的Km值。这明显是由于羧基对芳香环的诱导效应(去活化效应)。该效应可以通过修饰羧基，如通过用醇酯化抵销。优选的醇是甲醇，乙醇和异丙醇。甲基，乙基和异丙基酯与酶相联系进行检验，这些物质表现出比3,4-DABA有显著提高的特性。特别是发现乙酯有非常高的V最大，即在相同的浓度下它有比OPD更高的反应速度。
具有，例如过氧化氢的、有酶或无酶的OPD的氧化反应机制用下列反应式描述。
Figure A9719860100092
从这里可以看出，氧化产物是2,3-二氨基吩嗪。
当利用这里所描述的化合物中的一种时，氧化产物也是氨基吩嗪。对于3,4-DABA，其氧化产物是4,7-二羧基-1,2-二氨基吩嗪，如下式所示。
Figure A9719860100101
       3,4-DABA                  4,7-二羧基-1,2-二氨基吩嗪
为了反应能够发生，底物在3,4-位上应有两个氨基。然而，如果羧基不妨碍反应，在2,3-位或2,3,4-位上有氨基的底物也可以被利用。
在对位有氨基的底物也可以用于产生有色产物。其中的一个例子是3,6-DABA。
为了抵销羧基的诱导效应(即由于基团对电子的吸引效应引起的芳香环的去活化作用)，利用供电子基团研究了羧基的酯化，察看在保留非诱变属性的同时能否抵销去活化作用。为了研究不同烷基对物质的酶特性和可能的诱变特性的影响，合成了3,4-DABA的甲基，乙基和异丙基酯。
具有通式Ⅰ的化合物优选地溶解于DMF(二甲基甲酰胺)中，但其它的有机溶剂也可用于这个目的。如果具有通式Ⅰ的化合物是盐的形式，它可以溶解于水，但用有机溶剂时这种形式是优选的。
在另一个方面，本发明涉及一种定量和/或定性分析具有生物重要性的物质的方法。在这种情况下，带有标记物的过氧化物酶与所讨论的化合物结合。过氧化氢则在过氧化物酶存在的条件下用生色底物(即产生颜色的化合物1转化，该底物包括与通式Ⅰ连接的键。
在本发明方法的一个优选的实施方案中，利用了下列底物的一种：氨基苯甲酸的甲基，丙基或异丙基酯。
在具有生物重要性的物质是抗原的情况下，利用相关的抗体。在这一点上，技术人员会联想到其它的组合。
通过本发明的方法产生的有色产物特别适合于染纺织品、线、纱、羊毛、皮革和毛皮及人的头发。其它诸如棉花和丝之类的天然纤维及诸如多胺、聚氨基甲酸乙酯和聚酯之类的合成纤维也可以用该产物染色。
有色产物可以在用于染色之前立即制成，也可以在紧邻待染物的地方合成。例如这可以通过将底物和氧化系统在人的头发上混合来进行。
染色操作可以通过用本发明的底物和过氧化氢或氧化酶的混合物漂洗头发进行。加入过氧化物酶并使之分布在头发上。当得到所需的着色程度时用水漂洗头发。
底物可以在施用于头发之前和氧化系统混合。如上所述，底物可以在过氧化物酶的存在下用过氧化氢或产生过氧化氢的氧化酶氧化。
过氧化物酶属于已知称作氧化还原酶的酶类。该酶类还包括脱氢酶类、加氧酶类、氧化酶类、漆酶和相关酶类。这些酶也可作为氧化系统/氧化剂用于，例如，染角质纤维，诸如头发、羊毛、皮毛和皮革之类的。染色组合物和优选的氧化酶下面有进一步的描述。
在由过氧化物酶催化的氧化反应中，氧供体是用作电子受体的过氧化氢。氧化酶利用氧作为电子受体。
合适的氧化酶的例子包括儿茶酚氧化酶、漆酶和邻-氨基酚氧化酶。
因此从这一点上说，可以用于底物氧化反应的氧化系统包括过氧化物酶和过氧化氢，还包括氧化酶、漆酶和相关酶及氧。当系统仅由氧化酶和氧组成时，仅需要将氧化酶加到底物中，因为空气中的氧作为氢化剂。染色组合物
从一个方面说，本发明涉及一种特别适合于染包括诸如头发、皮毛、皮革或羊毛之类的角质纤维的组合物。该组合物包括：1)至少一种氧化酶，2)至少一种由式1所定义的底物和可有可无的3)至少一种修饰剂。
该组合物的优选的用途是作为染人类头发的永久染色剂。
氧化酶也如上所述是一种氧化还原酶，即分类在根据国际生化和分子生物学(IUBMB)联盟的建议(1992)的酶分类号E.C.1(氧化还原酶)下能催化氧化还原反应的酶。
在氧化还原酶类中，通过作用于氧(O2)和/或作为受体的过氧化物催化底物(电子或氢供体)氧化的酶是优选的酶。这种酶包括分类在含有氧化酶，包括E.C.1.1.3,E.C.1.2.3,E.C.1.3.3,E.C.1.4.3,E.C.1.5.3,E.C.1.7.3,E.C.1.8.3和E.C.1.9.3,E.C.1.10.3中的漆酶和相关酶，及E.C.1.11.中的过氧化物酶的酶类中的酶。
根据本发明，特别考虑到三种类型的氧化还原酶：a)漆酶或相关酶，它作用于分子氧，产生水(H2O)，不需要过氧化物(如H2O2)，b)氧化酶，它作用于分子氧(O2)，产生过氧化物(H2O2)，和c)过氧化物酶，它作用于过氧化物(如H2O2)，产生水(H2O)。
还考虑到包含来源于三种类型的酶类中单一或不同酶类的多种酶组合的酶系统。在本说明书中，虽然为了简便，通常只提及一种酶，但应当理解，这些描述通常适用于这样的一种以上的酶的组合。另外，虽然本发明总体上描述了和染发相关的优选的方面，但应当理解，这些描述一般适用于适于染其它类型角质纤维的根据本发明的组合物。
特别优选的酶是漆酶及相关酶，术语“漆酶及相关酶”包括酶分类E.C.1.10.3.2(漆酶)所包含的酶和E.C.1.10.3.1所包含的儿茶酚氧化酶，酶分类E.C.1.3.3.5所包含的胆红素氧化酶和酶分类E.C.1.14.99.1所包含的多酚单加氧酶。漆酶是含多-铜的催化酚类和芳香胺氧化的酶。漆酶-介导的氧化导致由适宜的酚底物产生芳氧基中间体；这样所产生的中间体的最终偶联提供了二聚、寡聚和多聚反应产物的组合。某些反应产物可用于产生适合染发的染色剂。
优选地，所用的漆酶可以来源于多孔菌物种(特别是P.pinsitus或变色多孔菌)，毁丝霉物种(特别是嗜热毁丝霉)，丝核菌物种(特别是Rh.praticola或立枯丝核菌)，Rhus物种(特别是Rhus vernicifera),Pyricularia物种(特别是P.oryzae)，或蛾柱霉物种(特别是嗜热蛾柱霉)的菌株。
在本发明的特定的实施方案中，氧化还原酶是诸如多孔菌物种的漆酶。漆酶，特别是在WO96/00290中描述的Polyporus pinisitus漆酶(也称为Trametes villosa漆酶)(来自于Novo Nordisk生物技术公司)或毁丝霉物种的漆酶，特别是WO95/33836中描述的嗜热毁丝霉漆酶(来自于Novo Nordisk生物技术公司)。
此外，漆酶可以是蛾柱霉物种的漆酶，如WO95/33837和WO97/19998中所描述的嗜热蛾柱霉的漆酶(来自于Novo Nordisk生物技术公司)，其内容本文一并参考，或Pyricularia物种的漆酶，如可以从SIGMA买到的商品名为SIGMA NO.L5510的Pyricularia oryzae漆酶，或鬼伞物种的漆酶，如鬼伞漆酶，特别是灰盖鬼伞IFO30116漆酶，或丝核菌物种的漆酶，如立枯丝核菌漆酶，特别是在6.0到8.5范围之内有pH最适值的、在WO95/07988中描述的中性立枯丝核菌漆酶(来自于Novo Nordisk A/S)。
漆酶也可来源于真菌，如金钱菌属，层孔菌属，香菇属，侧耳属，曲霉属，脉孢菌属，柄孢壳属，射脉菌属，例如射脉菌(WO92/01046)，云芝物种，如C.hirsitus(JP2-238885)，或葡萄孢属。
胆红素氧化酶优选地来源于漆斑菌物种的菌株，如M.verrucaria。
根据本发明的染色组合物底物(即染料前体)可以是上面在通式Ⅰ定义内的任何一种。
优选的染料前体(即底物)是苯甲酸酯，特别是二氨基苯甲酸酯，特别是3,4-二氨基苯甲酸甲酯(DABA-Me),3,4-二氨基苯甲酸乙酯和3,4-二氨基苯甲酸异丙酯。其它氧化剂
底物也可被一些无机化合物氧化，其中包括次氯酸盐(CIO-)、次溴酸盐(BrO-)、高锰酸盐(MnO4 -)、重铬酸盐(Cr2O7 2-)和铁离子(Fe3+)。
氧化体系可以认为本身就是氧化剂，或者是酶和氧化剂的组合。修饰剂
典型地掺入染色组合物中的修饰剂包括间-芳香二胺、间-氨基苯酚、多酚、氨基萘或萘酚。修饰剂(成色剂)在氧化酶等存在的情况下和染料前体反应，将其转化为有色化合物。特定修饰剂(成色剂)的例子包括间-苯二胺、2,4-二氨基苯甲醚、1-羟基萘(α-萘酚)、1,4-二羟基苯(对苯二酚)、1,5-二羟基萘、1,2-二羟基苯(邻苯二酚)、1,3-二羟基苯(间苯二酚)、1,3-二羟基-2-甲苯、1,3-二羟基-4-氯苯(4-氯间苯二酚)、1,2,3-三羟基苯、1,2,4-三羟基苯、1,2,4-三羟基-5-甲苯和1,2,4-三羟基甲苯。染角质纤维的方法
在另一方面，本发明涉及一种用上述组合物染角质纤维，特别是头发、皮毛、皮革和羊毛的方法。染色方法可以用一种或多种染料前体(即本发明的底物)并可有可无地与一种或多种修饰剂结合进行。染料前体和用在本发明组合物中的其它成分的量和通常的商品量相一致，因此为本领域技术人员所知。染发典型地是在或接近室温下，优选的是在所用酶的最适温度附近，和在3.0到9.0，优选的是4.0到8.5，特别是6.0到8.0范围的pH下进行。染料前体(即本发明的底物)和可有可无的修饰剂如上所述。
本发明用下列非限制性实施例进一步描述。实施例13,4-二氧基苯甲酸酯的合成
由4-氨基-3-硝基甲苯合成酯，接着酯化并还原4-氨基-3-硝基苯甲酸酯为3,4-二氨基苯甲酸酯。反应如下所示：
Figure A9719860100141
3,4-DABA酯的制备
4-氨基-3-硝基甲苯中的氨基通过在无水乙酸中煮沸加以保护。甲基在含有硫酸镁的水溶液中用高锰酸盐氧化。乙酰基通过用0.1盐酸煮沸除去。分离和干燥后，将4-氨基-3-硝基苯甲酸溶解于无水醇中，并加入浓硫酸。经煮沸2到5小时使酸基酯化。确切的煮沸时间依醇的类型而定。最后一个步骤是用活性铁和水在煮沸的苯里将分离产物还原约5小时。
当反应完全时，滤出铁颗粒，残留物在无水硫酸钠上干燥24到48小时。过滤和蒸发后，酯在正丁醇和苯比例为1∶10的混合物中重结晶。
上述步骤用于产生用于酶的测定和诱变检验的3,4-DABA酯。如果以合理的价格需要大量的3,4-DABA酯，则3,4-DABA的直接酯化将是优选的。因此甲酯可以通过往含有甲醇的3,4-DABA溶液里通氯化氢气体来制备。这最后一种方法只限于乙酯的生产，不能用于生产异丙酯。3,4-DABA酯的表征薄层层析
对所制备的3,4-DABA酯进行分析，并利用MERCK 60 F254型，浓缩区的库存号(the stock number of the zone of concentration)为5583的硅胶板借助于薄层层析(TLC)进行比较。用氯仿、甲醇和乙酸体积比为90∶5∶5的混合物作为溶剂。为便于比较，OPD和3,4-DABA在同一板上进行分析。所得的Rf值如表1所示。
表1
化合物 Rf值
3,4-DABA 0.15
OPD 0.19
甲酯 0.29
乙酯 0.31
异丙酯 0.33
从表1中可以看出较大的烷基基团在含有氯仿的溶剂中有可测程度较大的置换。如所预料的，可以看出置换最少的是含有自由羧基的3,4-DABA。所检验的所有的组合都以斑的形式移动，该斑表明它们的纯度。
当配制底物的溶液时，就水中溶解性而言，3,4-DABA酯是类脂类的事实是没有问题的。二甲基甲酰胺的标准溶液用pH为5.0的含水缓冲液稀释。通过酶的作用形成的高浓度的底物氧化产物可导致溶液中轻微的混浊。用1M硫酸将pH降低到约1，产生完全清亮的溶液。这是由于氨基中质子的加入。熔点的确定
为了证实所合成的物质和文献中所述的相同，确定了它们的熔点，并和Chapmen和Hall有机化合物词典，第二版，2卷中1532页上的表中所给的值进行比较。熔点用硅油浴通过毛细管方法确定。
熔点在表2中给出。
表2
物质 测定的熔点 文献中的值
--甲酯 108-109℃ 108-109℃
--乙酯 112-113℃ 112-113℃
--异丙酯 73-74℃ ---
从上表中可以看出由实验所测定的熔点和文献中给定的熔点之间有很接近的一致性。因此，我们有理由假设合成的物质和文献中所述的物质是相同的。在文献中找不到异丙酯的熔点值。紫外光谱
测定了OPD以及甲酯、乙酯和异丙酯的UV光谱。
用化合物的甲醇溶液进行了从360nm到210nm的扫描。浓度为0.1/1。表3说明了所测化合物的吸收最大值和消光系数。
表3
物质 吸收最大值 消光系数
OPD 290.0nm231.3nm 2000M-13400M-1
-甲酯 310.0nm277.5nm232.5nm 6000M-16000M-18400M-1
-乙酯 310.0nm277.Snm232.5nm 6200M-16000M-18600M-1
-异丙酯 310.0nm277.5nm232.5nm 6500M-16200M-18700M-1.
由上表可以看出所有三种酯在相同的波长处有吸收。在237.5处随着烷基分子量的增加消光系数略有增加。3,4-DABA酯在277.5处表现出典型地最大值。由于酯羰基基团使得该最大值在OPD中没有发现。
为了研究3,4-DABA和三种酯被过氧化物酶催化的氧化特性，对与浓度不断增加的底物的酶反应起始速度进行了一系列测定。对OPD、3,4-DABA、3,4-DABA甲酯、3,4-DABA乙酯和3,4-DABA异丙酯进行了测定。
用在492nm处的吸收作为反应过程的量度。将过氧化物酶加入到混合于pH5.0缓冲液中的底物和过氧化氢混合物2分钟后，将混合物在492nm处吸收值看作起始速度。选择492nm的波长是因为它用于OPD的标准测定过程。没有一个底物在这个波长处有特别高的吸收。
通过在改变底物的浓度的同时测定反应的起始速度，有可能将Michaelis/Menten等式用于体系。
在理想的条件下，实验测得的值将接近以下表达式的值：
Figure A9719860100181
[S]其中[S]表示底物的浓度，V最大表示在具体测定中所达到的最大起始速度。Km定义为V最大/2时的底物浓度。因此小的Km值是低浓度底物使酶饱和的酶体系的特征。
该表达式意味着随着底物浓度的增加起始速度会增加，但速度曲线会变得平坦，非常高的底物浓度时达到Vmax。实际上，参数Kkat可以计算为Vmax/[E]，其中[E]是反应中酶的摩尔浓度。Kkat与min-1相同，反映饱和溶液中的酶对底物的活性。
在过氧化物酶体系能由上述公式描述的不到一分钟的短时间内，过氧化物酶体系有一个非常复杂的能量平衡(Arnoa等，(1990))。实施例2酶促测定配制下列溶液用于酶测定。a)测定缓冲液50mM、pH为5.0的磷酸盐/柠檬酸盐缓冲液通过混合50mM的Na2HPO4溶液和50mM的柠檬酸溶液配制。混合过程中测定pH。b)1∶10稀释的DMF用移液管吸10mL置于有刻度的烧瓶中，用测定缓冲液定容至100mL。c)0.018％过氧化氢溶液15μL的30％过氧化氢溶液(PERHYDROL,Merck)用25mL测定缓冲液稀释。d)过氧化物酶的稳定缓冲液过氧化物酶的稳定缓冲液，即稳定该酶的缓冲液根据Olsen和Little(1983)的方法制备。0.1M的醋酸钠缓冲液或0.5M的CaCl2，调pH至5.6。37.5mg N-乙酰-三甲基-溴化铵溶于75mL缓冲液。该溶液中加入25mL甘油。因为在该缓冲液中酶分子的聚集被阻止，所以酶活性得以维持。e)过氧化物酶的标准溶液：10mg辣根过氧化物醇Ⅵ-A型(Sigma产品号6782)溶于10mL稳定缓冲液。贮存于-15℃。它可以保存数月(Olsen和Little(1983))。f)过氧化物酶的实验溶液标准过氧化物酶溶液1∶1000稀释，10mL测定缓冲液加到10μL标准溶液中。g)底物的标准溶液0.5mM的每种底物溶于5mLDMF。这些溶液于-15℃保存数周。h)底物的实验溶液标准溶液用测定缓冲液以1∶10稀释。用前底物溶液以1∶10稀释。0.5mL标准溶液用4.5mL测定缓冲液稀释。作为底物浓度函数的反应速度的测定
加入100μL稀的过氧化物酶溶液(实验溶液)1分钟后，对于OPD、3,4-DABA及3,4-DABA的甲酯、乙酯和异丙酯中每种化合物进行了15次测定，492nm处每种情况下测定两次光吸收值。在整个研究过程中，过氧化物酶的浓度维持在50ng/mL。通过利用表4中给出的底物体积和10体积-％DMF溶液的体积，有可能利用恒定的反应体积和恒定的DMF浓度。对于所有的测定，共用1550μL缓冲液和50μL过氧化物酶的实验溶液。于是总体积如下：300μLDMF和底物溶液，1550μL缓冲液，100μL过氧化物酶的实验溶液和50μL过氧化氢溶液。总共2000μL。
表4
μL底物浓度 μL10％DMF溶液 底物浓度(μmol/L)
0 300 0
5 295 25
10 290 50
15 285 75
20 280 100
25 275 125
30 270 150
35 265 175
40 260 200
50 250 250
60 240 300
80 220 400
100 200 500
150 150 750
200 100 1000
300 0 1500
表5包含有关5种化合物所测得的Km、V最大和Kkat值的信息。
表5
底物 Km(μmol/μL) V最大(分钟-1) Kkat(1*mol-1*分钟-1)
OPD 47.35 0.16 1.6*108
3,4-DABA 251.22 0.20 2.0*108
-甲酯 125.97 0.22 2.2*108
-乙酯 212.39 0.27 2.7*108
-异丙酯 118.46 0.22 2.2*108
起始速度的测定结果以光吸收的单位表示，而不以摩尔单位表示。为了能够测定反应的“真实”速度，有必要分离每种底物的氧化产物，确定摩尔消光系数。Kkat值以1mol 50000g/mol的过氧化物酶计算。
图1-5是表示OPD、3,4-DABA、3,4-DABA甲酯、3,4-DABA乙酯和3,4-DABA异丙酯的起始速度测定结果的图。
如表1和图1到6所示，3,4-DABA的羧基酯在过氧化物酶/过氧化氢体系中是有效底物。用这些化合物可能得到比OPD更高的起始速度。在所讨论底物的酶测定中由于Km确实只表示低浓度底物时体系的敏感性，它本身是有效性的较差的指示参数。实际上，可以选择底物浓度以用不同的酶浓度促进最大和线性颜色的产生。也就是说，V最 大和Kkat对于不同底物的比较来说是更为相关的参数。已发现，对于所研究的所有酯，V最大和Kkat值都可观地大于OPD的可比性值。
所有反应速度以光吸收的单位表示，部分由于大多数实际的酶测定都是以光吸收的测定为基础的，部分由于反应产物不从反应混合物中分离。实施例3化合物诱变性的测定
利用Ames检验(Maron和Ames(1983))确定化合物的诱变特性。如Venitt和Parry(1984)所述的方法制备营养介质。往3×2mL的熔化琼脂(4)中加入100μL50、100和200mM的溶于DMSO的化合物溶液。用移液管取100μL生长好的Salmonella tphimurium TA98(BIO-TEST gl.skolevej 47,6731 Tiareborg)培养物加入相同的试管。该细菌含有组氨醇脱氢酶基因的移码突变，其生长需要组氨酸。诱变性芳香胺能将该细菌突变为His+，因此能在营养介质上生长。温育后的菌落数因此可给出加入化合物致突变能力的定量的量度。在所有的实验中，不存在诱变剂时发生自然突变。这些提供了“背景”突变的量度。
OPD不是直接诱变剂，它必须首先被肝酶体系P450活化。因此所有实验都在加入或不加入包含P450体系之大鼠肝“S9-混合物”的情况下进行。每支试管加0.5mL“S9-混合物”。突变的标准是增加待测化合物的浓度时，有His+突变体数目的显著增加。这些实验的结果在图7-11中给出。从该图可以看出只有OPD具有诱变特性。实施例4本发明染料前体的染色效果
利用0.05mg活性酶蛋白嗜热毁丝霉(Myceliophthora thermophila)漆酶(可从NOVO Nordisk得到和在WO95/33836中有所描述)每mL反应混合物检测了不同染料前体的永久氧化染色效果。所检测的染料前体是：0.1M磷酸钾缓冲液，pH7.0中的0.1％w/w3,4-二氨基苯甲酸(DABA)。0.1M磷酸钾缓冲液，pH7.0中的0.1％w/w3,4-二氨基苯甲酸甲酯(DABA-Me)。所用修饰剂：0.1M磷酸钾缓冲液，pH7.0中的0.1％w/w间-苯二胺(MPD)。染料前体溶液通过混合指定的修饰剂制备，以使染色溶液中的终浓度是：染料前体(即本发明的底物)为0.1％w/w，修饰剂为0.1％w/w。染发
使用1克6″De Meo纯自然白发束(美国De Meo Brothers公司)。
用涡旋混合器将4mL染料前体溶液(包括修饰剂)和1mL漆酶混合，施用于发束上，30℃温育30分钟。
发束用流动水冲洗，用香波洗，用水漂洗，梳理，空气干燥。
用色度计测定a*、b*和L*，然后如下所述计算ΔE*。
未经酶处理的发束样品用来作为空白。
检验结果如表6所示。
表6
含/不含MPD的DABA和DABA-Me 评定
0.1％w/w染料前体/修饰剂 ΔL Δa Δb ΔE
DABA -4.27 -0.63 -2.55 5.01 无颜色
DABA+MPD -23 -2.21 -18.29 29.47 浅灰色
DABA-Me -7.58 6.53 -2.14 10.23 浅橙色
DABA-Me+MPD -32.31 2.35 -25.07 40.96 浅灰紫色
头发颜色的评定
用Minolta CR200色度计通过利用参数L*(“0”=黑，“100”=白)、a*(“-”=绿，“+”=红)和b*(“-”=蓝，“+”=黄)定量地测定头发颜色。
ΔL*、Δa*和Δb*是分别和未被处理头发的L*、a*和b*相比的L*、a*和b*差值(如ΔL*=L* 样品-L* 未被处理头发)。
ΔE*以ΔE*=平方根(ΔL*2+Δa*2+Δb*2)计算，表示总的定量的颜色变化。实施例5DABA-Me和各种修饰剂的染色效果
除了使用0.2％w/w染料前体和0.2％修饰剂外，全按照实施例4中描述的步骤检验具有各种修饰剂的染料前体(即底物)DABA-Me的永久染色效果。
表7
0.2％DABA-Me和0.2％w/w修饰剂 ΔL* Δa* Δb* ΔE* 评定
4-氯间苯二酚 -22.36 1.19 -6.28 23.26 灰-绿
5-氨基-邻-甲酚 -14.1 5.69 -2.1 15.35 浅橙色
间-苯二胺 -33.25 2.17 -23.71 40.9 灰色(带蓝色的)
焦棓酚 -29.47 5.74 -7.69 30.99 棕色
4-甲氧基-1,3-苯二胺 -39.24 2.33 -19.73 43.98 棕-灰/黑
可以看出角质纤维可以用DABA-Me和修饰剂染色。

Claims (20)

1．一种经氧化产生颜色的底物，其特征在于其包含具有通式Ⅰ的氨基苯甲酸化合物：
Figure A9719860100021
其中R是氨基、单-或分布的氨基或OR’，其中R’是H、烷基、链烯基、炔基，卤代烷基、硝基、苄基、苯基或取代苯基，X、Y和Z可以各自分别是氢、烷基、链烯基、炔基，卤代烷基、硝基、苄基、苯基、取代苯基、氨基、羟基或巯基，其前提是基团X、Y和Z中至少有一个是氨基或其盐。
2．根据权利要求1的底物，其中的R’是甲基、乙基或异丙基酯。
3．具有通式Ⅰ的氨基苯甲酸化合物及其盐在基于使用过氧化物酶的分析中作为产生颜色的底物的用途。
4．具有通式Ⅰ的氨基苯甲酸化合物及其盐在染发组合物及包括纺织品、线和纱在内的天然和合成纤维之组合物的染色中作为产生颜色的底物的用途。
5．根据权利要求3或4的用途，其中的化合物选自氨基苯甲酸的甲基、乙基或异丙基酯。
6．具有生物重要性的物质的定量和/或定性分析方法，其中带有标记物的过氧化物酶物与目的化合物结合，然后在过氧化物酶存在下过氧化氢通过产生颜色的底物转化，其特征在于使用选自具有通式Ⅰ的苯甲酸化合物及其盐的底物。
7．根据权利要求6的方法，其中的化合物选自氨基苯甲酸的甲基、乙基或异丙基酯及其盐。
8．根据权利要求6的方法，其中的过氧化物酶标记物能够和具有生物重要性的物质形成免疫连接。
9．根据权利要求6的方法，其中的具有生物重要性的物质是抗原，标记物是针对抗原的抗体。
10．产生有色产物的方法，其中根据权利要求1或2的底物通过氧化体系转化。
11．根据权利要求10的方法，其中的氧化体系包括一种无机化合物，优选的是化合物次氯酸盐、次溴酸盐、高锰酸盐、重铬酸盐或铁Fe3+中的一种。
12．根据权利要求10的方法，其中的氧化体系包括一种酶和一种电子受体。
13．根据权利要求12的方法，其中的酶是过氧化物酶，电子受体是过氧化氢或酶是氧化酶，电子受体是氧。
14．根据权利要求13的方法，其中的氧化酶选自邻苯二酚氧化酶、漆酶和相关酶邻-氨基酚氧化酶。
15．适于染角质纤维的组合物，其包含1)至少一种氧化酶，2)至少一种根据权利要求1或2任何一项的底物，和可有可无的3)至少一种修饰剂。
16．根据权利要求15的组合物，其中的氧化酶是选自漆酶和相关酶、氧化酶或过氧化物酶的氧化还原酶。
17．根据权利要求16的组合物，其中的氧化酶是漆酶，特别是来源于多孔菌物种的菌株，特别是P.pinsitus或变色多孔菌的菌株，毁丝霉物种的菌株，特别是嗜热毁丝霉，丝核菌物种的菌株，特别是Rh.praticola或立枯丝核菌，Rhus物种的菌株，特别是Rhus vernicifera的菌株的漆酶，或来源于蛾柱霉属的菌株，特别是嗜热蛾柱霉，Pyricularia物种的菌株，特别是P.oryzae的漆酶。
18．染角质纤维的方法，该方法包括将角质纤维与包含1)至少一种氧化酶，2)至少一种根据权利要求1或2的底物，和可有可无的3)至少一种修饰剂的组合物在足以允许底物氧化为有色化合物的条件下接触一段时间。
19．根据权利要求18的方法，其中在3.0到9.0，优选的是4.0到8.5，特别是6.0到8.0的pH范围内进行染色。
20．根据权利要求18或19的方法，其中的组合物如权利要求15至17中任何一项所定义。
CN97198601A 1996-10-08 1997-10-08 作为染料前体的二氨基苯甲酸衍生物 Pending CN1232384A (zh)

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CA2265734A1 (en) 1998-04-16
DE69718351D1 (de) 2003-02-13
WO1998015257A1 (en) 1998-04-16
US6231621B1 (en) 2001-05-15
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US20020004958A1 (en) 2002-01-17

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