CN1653189B - 制备聚合物涂层的方法 - Google Patents
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Abstract
本发明涉及一种在载体上通过光聚合一种可光聚合的液体组合物来制备聚合物涂层的方法，一种用于在载体上制备聚合物涂层的合适的装置，和一种用于制备其中置入了指示剂的传感器的方法。
Description
本发明涉及一种在载体上通过可聚合的液体组合物的光聚合而制备聚合物涂层的方法，一种适于在载体上制备聚合物涂层的装置以及一种用以制备含有其中掺入了指示剂的聚合物涂层的传感器的方法。
在载体上制备聚合物涂层是已知的技术。为此需要将可聚合的液体尽可能以均匀的厚度施涂于载体上并进行完全的聚合。该聚合过程可以通过化学聚合引发剂或是通过对液体进行照射而引发。
有关粘合剂膜制备的聚合技术是已知的，其中要将官能化的丙烯酸酯预聚物的混合物施涂于载体上，然后通过照射聚合物物料表面进行完全地或部分地硬化。聚合物涂层厚度的控制可通过选择光照强度和持续时间以及通过所用预聚物的自吸收性来实现。
现有技术方法的缺点在于，通常需要很高昂的成本来调节载体上预定的和均匀的聚合物涂层厚度。此外，在传统的聚合反应方法中，人们常常发现聚合物涂层在载体上的粘结力非常小。
因此本发明的任务在于至少部分地克服所述的现有技术的缺陷，特别是提供一种在载体上制备聚合物涂层的方法，该方法能较为简单地制备得到具有预设的和均匀的涂层厚度的聚合物涂层。
与现有技术中记载的有关制备粘合剂的方法(在该方法中制备的是封闭且疏水的聚合物涂层)相反，所制备出的应是开放的、且能吸收含水试样液体和分析物的亲水涂层。
该任务可以通过如下方法得以解决，即将一种液态可聚合组合物施涂在载体上，并且直接在载体上进行聚合，但是不是完全聚合而只是在具有预设厚度的层中进行聚合。以这种方法就能简单地制得均匀且很好地粘附于载体上的涂层载体。
因此本发明内容在于一种在透明载体上制备聚合物涂层的方法，包括如下步骤：
(a)提供载体，
(b)将可光聚合的液体组合物施涂于载体上，
(c)透过载体照射可光聚合的液体组合物，照射方式是使液体组合物只进行部分的聚合反应且在载体上形成具有预设厚度的聚合物层，和
(d)从聚合物涂层上去除残留的液体组合物。
用以制备聚合物涂层的载体是一种至少部分光学透明的载体，例如塑料载体如聚碳酸酯膜、醋酸纤维素膜、聚酯膜或聚醚膜，玻璃载体或石英载体。也可以使用复合材料制成的载体。当使用这种至少部分光学透明的载体时，优选透过载体对液体组合物进行照射。载体厚度的选择较好地是一方面使得聚合物涂层具有足够的机械稳定性，而另一方面要使得用来照射的光线具有足够的透过度。例如，所用载体的厚度可以为5μm至20mm。同样还优选使用透射UV的载体。
可光聚合的液体组合物含有至少一种可光聚合的物质，即通过光照(必要时可以在有光引发剂存在的条件下)能聚合的物质。这类物质的优选例子是可光聚合的单体，如烯属不饱和物质，即带有C＝C-键的物质。合适的可光聚合的物质的其他实例是官能化的且在光照下能交联的低聚物或高聚物。这类光活性的官能化产物包括例如丙烯酸酯、叠氮化合物、卡巴肼、砜叠氮化合物(Sulfonazide)、重氮甲酮、二甲基顺丁烯二酰亚胺、可光致环化的基团(如查耳酮)和Benophen衍生物。合适的低聚物或高聚物是例如聚氨酯、聚乙烯醇、聚酯、聚醚、聚乙烯基吡咯烷酮、聚丙烯酸酯或低聚糖。特别优选的是选自如下一组的可光聚合的物质，例如丙烯酸类单体，如丙烯酰胺，丙烯酸酯如聚二丙烯酸乙二醇酯，乙烯基芳族单体，如4-乙烯基苯磺酸，官能化的聚乙烯基吡咯烷酮和一种或多种上述物质的任意结合。
在一优选实施方式中，所用的含水可聚合组合物中，待聚合的单体以溶解的形式存在。因此，对于该实施方式较为理想的是使用在含水溶剂中具有足够高溶解性的亲水单体。
液态组合物中聚合反应的引发可以由光照来实现。为启动聚合反应，优选组合物中含有一种或多种光引发剂。合适的光引发剂的例子有自由基引发剂如苯甲酮、联苯酰、蒽醌、硫代磺酸、偶氮化合物，或是离子引发剂如三芳基锍盐、六氟锑酸芳鎓(Aryliumafluoroantimonate)。
透过载体对组合物进行光照，以使得聚合反应开始于载体表面并且--根据设定的聚合反应条件的不同--由于光被吸收于可聚合液体之内，从而在距载体表面一个预设的距离聚合反应终止。载体上水平层的翘曲或是偏离并不会影响聚合物涂层的厚度。机械公差可被进一步地消除。
聚合物涂层的厚度可以通过合适的措施在很宽的范围内进行调节。特别是聚合物涂层厚度能通过变化光照射强度，光照持续时间或/和向液体组合物中添加聚合反应的阻聚剂，例如UV吸收物质来控制。另外，也可以通过载体厚度或/和载体材料来实行控制。聚合物涂层的厚度优选为≤500μm且特别优选为≤100μm。如果将聚合物涂层用作传感器，特别是用作生物传感器，则常常也可制备更小的层厚度，优选≤50μm，特别优选≤5μm。
如果将聚合物涂层用作为传感器的成分，则其除了上述的成分外还应较为理想地包括指示剂，如能在包围着聚合物层的介质中对参数作出反应的光学和/或电化学指示剂。可以向指示剂中添加可光聚合的液体组合物或是--特别是当它们是小分子时--使指示剂分散到已制成的聚合物涂层中。如果聚合物层含有多种指示剂，则也可以将上述各种措施结合起来。
指示剂也可以是一种大分子，例如有着≥10kD特别是≥20kD的分子量。特别优选用作指示剂的是催化剂物质，例如在需要时能以酶-辅酶络合物形式存在的酶。特别优选的酶的例子是氧化还原酶，特别是脱氢酶，如葡萄糖脱氢酶(E.C.1.1.1.47)或氧化酶。辅酶优选是以共价键或非共价键连接在酶上且通过与酶底物的反应能变性如被氧化或还原的有机分子。优选的辅酶的例子是黄素衍生物、烟碱衍生物、醌衍生物，例如FAD，FADH2，NAD+，NADH/H+，NADP+，NADPH/H+或PQQ。
除了酶和必要时含有的辅酶外，聚合物层还含有媒剂，即具有再生辅酶作用的物质。在这种情况下酶就起到了催化指示剂的作用，即其能转化底物的多种分子，而这种底物是例如存在于所加试样中的分析物，如血液中的葡萄糖。
在一特别优选的实施方式中，聚合物涂层含有酶-辅酶络合物作为待验证的酶底物的化学计量反应物。这里的辅酶是一次反应不会再生。在该实施方式中不必再用到需要结合使用稳定性很小且易干扰性很高的复杂反应剂混合物的媒剂。
如果使用大分子的底物作为指示剂，则可以通过合适的聚合物交联作用(如通过使用二或/和多官能基单体)获得交联聚合物涂层，在该涂层中插入有固定形式的大分子指示剂物质，同时可以将低分子量的物质，如辅酶、酶底物等分散到该层中。
聚合物涂层的制备可以以连续工艺进行，其中在施涂于载体上的液体可光聚合的组合物上连续生成聚合物涂层。当进行连续的聚合反应时，优选在第一位置将可光聚合的液体组合物连续施涂于本身运动着的载体上，然后在第二位置上对其进行连续的光照。显而易见地，载体也可以保持静止，而施涂液体和光照的位置移动。同样也可考虑使用非连续的方法来生产聚合物膜。这些实施方式有一个共同点，即由于是透过载体对可光聚合的液体组合物进行照射，因此可以进行直接在载体上起动但并不完全的液体聚合反应。
本发明的再一个内容在于生产聚合物涂层的装置，其包括
(a)用于容纳且必要时还能用于运送载体的机构，
(b)用于将可光聚合的液体组合物施涂于载体上的机构，和
(c)用于透过载体照射可光聚合的液体组合物，从而能在载体上形成具有预定厚度的聚合物涂层的机构，和
(d)任选地，用于将未聚合的液体组合物从聚合物涂层上分离的机构。
所述方法和装置可用于生产一种其中的聚合物涂层中包埋有指示剂，例如生物分子，如酶的传感器。指示剂在聚合物涂层中可以以固定形式存在。特别优选指示剂是酶，必要时是以酶-辅酶络合物的形式。传感器可以是例如光学或/和电化学传感器。特别优选的传感器是基于荧光的传感器。
本发明的还一个内容在于制备传感器的方法，包括以下步骤：
(a)预备载体，
(b)将可光聚合的且含有至少一种指示剂的液体组合物施涂于该载体上，
(c)透过载体照射可光聚合的液体组合物，其照射方式使得在载体上形成具有预设厚度的聚合物涂层，
(d)从聚合物涂层中去除残留的液体组合物，和
(e)将具有含指示剂的聚合物涂层的载体置入传感器中，该传感器含有用以检测指示剂和试样中的分析物间的反应的机构。
所述检测机构优选是光学或/和电化学的检测机构。特别优选的又是光学检测机构，其包括用以照射聚合物涂层的光源和用以捕捉来自聚合物涂层的光的探测器。光源，例如激光或LED，优选设置成能使光透过载体照射到聚合物涂层中去。探测器优选设置成能捕捉到来自聚合物涂层的例如荧光发射的光线。
传感器可以用来确定任意分析物，例如物理化学参数，如温度，如O2、CO2、NOx等的气体分压，或者是用来确定生物化学参数，如生物试样中的被分析物，如体液。
另外，以下将通过附图和实施例来阐述本发明。
图1显示了通过本发明的方法制备得的传感器的第一种实施方式。在一种光学透明的载体(1)上施涂含有指示剂，如含有针对酶促反应的检测试剂的聚合物涂层(2)。再在聚合物涂层上放置试样(3)，如血液。可以通过光学方法来确定发生在含于试样(3)中的分析物和含于聚合物涂层(2)之间的检测试剂之间的酶促反应。来自光源(4)比如激光器或LED的光会从下方(透过载体)射入反应剂层(2)中。从试样上反射回来的吸收光或荧光可在探测器(5)中检测。必要时(特别是为检测荧光)在探测器之前接入一个光学过滤件(6)，用以抑制荧光激发光的串扰。
图2显示了本发明聚合物涂层的制备过程。在第一位置(13)，例如在一光学透明的载体(11)上，例如在一塑料膜上施涂液体试剂(12)。在第二位置上，利用来自光源(14)的光从下透过载体(11)照射液体试剂(12)。同时使载体沿着箭头所示方向(15)运动。于是在载体(11)上会直接形成聚合过的试剂层(16)。在聚合物涂层(16)上存在着过量的液体试剂。聚合好的试剂层(16)的厚度可以通过试剂组成、光照持续时间和强度以及通过载体(11)的性质来控制。
图3自下方示出了基于荧光的传感器的实施方式。例如通过图2的连续方法制得的且含有指示剂的聚合物涂层可以被切割，并利用已知技术埋入到传感器21中去。在将试样涂覆到上侧面之后，利用来自光源的激发光(23)，例如UV光从下方照射。通过分析物与检测试剂在聚合物涂层(22)中的反应而产生的荧光(24)例如蓝光能被探测器检测到。
也可将多种(相同或是不同的)反应物施涂于载体上。图4所示的就是盘形的这种实施方式的例子。在光学透明的载体(31)上可排布多个由带有指示剂的聚合物涂层组成的试剂点(32)。
实施例
实施例1：在聚合物膜中检测葡萄糖脱氢酶体系(GlucDH)NAD+中的葡萄糖
将如下物质的悬浮液混入塑料试剂瓶中。
配方1
| 物质 | 量[g] | 重量百分比[％] |
| 丙烯酰胺 | 2.5 | 22.02 |
| 亚甲基双丙烯酰胺 | 0.7 | 6.17 |
| 2，2-二甲氧基-2-苯基苯乙酮 | 0.05 | 0.44 |
| 甘油 | 5 | 44.05 |
| 甲基丙烯酸羟乙酯 | 1.4 | 12.33 |
| 甲基丙烯酸甲酯 | 0.4 | 3.52 |
| Crodasinic O溶液，pH8，0.3g/1000ml | 1 | 8.81 |
| N，N’-(1，2-二羟基亚乙基)双丙烯酰胺 | 0.3 | 2.64 |
| 总和 | 11.35 | 100 |
将0.5ml这种悬浮液和0.5ml GlucDH溶液(100mg/ml)相混合，并且混合物在超声波槽内进行无气泡的均匀混合。
将澄清溶液浇注到经电晕处理的膜(？)上并用常用的光照设备(Isel-UV-照射仪2)透过载体照射20min。然后用水短暂洗涤该膜并接着将其空气干燥。
这样所得到的层厚度为＜2μm。将新鲜调配的葡萄糖/NAD+溶液(GKL-3-溶液，300mg/d1葡萄糖，1ml/6.4mg NAD+)点在膜上。然后在UV灯下就能立即观察到很强的荧光。
实施例2：通过添加UV吸收剂影响层厚度
制备出其中含有蓝色颜料(吸收最大值≈650nm)用以更好识别的聚合物涂层(配方2)。在另一项试验中在初始配方中混入黄色颜料作为UV吸收剂(配方3)。
配方2
| 物质 | 量 | 重量百分比[％] |
| 丙烯酰胺 | 37.5g(0.53mol) | 25.78 |
| 聚二丙烯酸乙二醇酯，Mw≈575g/mol | 52.5g(约0.96mol) | 36.10 |
| Crodasinic O的溶液(0.3g/ll) | 50g | 34.38 |
| 4-乙烯基苯磺酸 | 5g | 3.44 |
| 光引发剂2，2-二甲氧基-2-苯基苯乙酮 | 350mg | 0.24 |
| 新制亚甲基蓝N | 100mg | 0.06 |
| 总和 | 145.45g | 100 |
通过搅拌和超声波槽处理将混合物混合均匀，用滴管将其分散在140μm的Pokalon膜(等离子处理，4级)上并置于UV照射仪(ActinaU4，W.Lemmen GmbH)上照射1min。
所得到的层厚度用螺旋测微器测量，为240.5μm。
配方3
| 物质 | 量 | 重量百分比[％] |
| 配方2 | 1ml | 约99.99 |
| 媒染黄7(686号)(UV吸收剂) | 0.0001g | 0.001 |
| 总量 | 约1.0001g | 100 |
将如上所述的混合物分布于膜上然后进行聚合。用螺旋测微器测量所得的层厚度为79.3μm。
试验结果表明，对层厚度的影响是可以实现的。如果没有UV吸收剂，在其他反应条件相同的情况下，层厚度为240.5μm(见上)；而有了UV吸收剂(媒染黄7)则只有79.3μm。
Claims (33)
1.一种在透明载体上制备聚合物涂层的方法，包括如下步骤：
(a)预备载体，
(b)将可光聚合的液体组合物施涂于载体上，
(c)透过载体照射可光聚合的液体组合物，其照射方式使得在载体上形成具有预设厚度的聚合物涂层，和
(d)从聚合物涂层上去除残留的液体组合物。
2.权利要求1的方法，其特征在于使用至少部分光学透明的载体。
3.权利要求1的方法，其特征在于使用厚度为至少5μm的载体。
4.权利要求1的方法，其特征在于使用选自塑料载体、玻璃载体或石英载体的载体。
5.权利要求1的方法，其特征在于使用一种可光聚合的液体组合物，该组合物包含有至少一种可光聚合的物质。
6.权利要求5的方法，其特征在于所使用的可光聚合的物质选自丙烯酸类单体、乙烯基芳族单体、官能化的聚乙烯基吡咯烷酮和它们的任意组合。
7.权利要求1的方法，其特征在于所用的可光聚合的液体组合物含有至少一种光引发剂。
8.权利要求1的方法，其特征在于通过变化以下三种变量来控制聚合物涂层厚度：
(i)照射强度，
(ii)照射持续时间，和/或
(iii)添加能吸收聚合反应光的物质。
9.权利要求1的方法，其特征在于所制得的聚合物涂层厚度为≤500μm。
10.权利要求9的方法，其特征在于所制得的聚合物涂层厚度为≤5μm。
11.权利要求1的方法，其特征在于所制备得的聚合物涂层含有至少一种指示剂。
12.权利要求11的方法，其特征在于使用大分子物质作为指示剂。
13.权利要求11的方法，其特征在于使用催化性物质作为指示剂。
14.权利要求13的方法，其特征在于所述催化性物质是酶。
15.权利要求1的方法，其特征在于制备交联的聚合物涂层。
16.权利要求15的方法，其特征在于交联聚合物涂层中包含大分子。
17.权利要求1的方法，其特征在于使用UV光进行照射。
18.权利要求1的方法，其特征在于聚合反应以连续过程进行。
19.权利要求18的方法，其特征在于在第一位置将可光聚合的液体组合物连续施涂于本身运动着的载体上，然后在第二位置上对其进行连续的光照。
20.一种用于制备聚合物涂层的装置，其包括：
(a)用于容纳且必要时还能用于运送载体的机构，
(b)用于将可光聚合的液体组合物施涂于载体上的机构，
(c)用于透过载体照射可光聚合的液体组合物，从而能在载体上形成具有预定厚度的聚合物涂层的机构。
21.权利要求20的装置，其还包括
(d)用于将未聚合的组合物从聚合物涂层上脱除的机构。
22.权利要求1至19之一的方法或权利要求20或21的装置用于生产其中聚合物涂层含有至少一种指示剂的传感器的用途。
23.权利要求22的用途，其特征在于指示剂在聚合物涂层中以固定形式存在。
24.权利要求22或23的用途，其特征在于聚合物涂层中含有酶。
25.权利要求24的用途，其特征在于聚合物涂层中含有的酶以酶-辅酶络合物的形式存在。
26.权利要求22或23的用途，其特征在于传感器选自光学或/和电化学传感器。
27.一种用于制备传感器的方法，其包括如下步骤：
(a)预备透明载体，
(b)将可光聚合的且含有至少一种指示剂的液体组合物施涂于载体上，
(c)透过载体照射可光聚合的液体组合物，其照射方式使得在载体上形成具有预设厚度的聚合物涂层，
(d)从聚合物涂层中去除残留的液体组合物，
(e)将具有含指示剂的聚合物涂层的载体置入传感器中，该传感器含有用以在试样中检测指示剂和分析物的反应的机构。
28.权利要求27的方法，其特征在于指示剂包含酶。
29.权利要求28的方法，其特征在于指示剂包含的酶以酶-辅酶络合物的形式存在。
30.权利要求28的方法，其特征在于检测机构包含光学或/和电化学检测机构。
31.权利要求30的方法，其特征在于光学检测机构包含用于照射聚合物涂层的光源和用于捕捉来自聚合物涂层的光的探测器。
32.权利要求31的方法，其特征在于设置光源使得光能透过载体照射入聚合物涂层中。
33.权利要求31或32的方法，其特征在于设置探测器用以捕捉来自聚合物涂层的荧光发射。
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10221846.3 | 2002-05-16 | ||
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| CN (2) | CN1653189B (zh) |
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