Bacteria-mediated lithography of polymer surfaces
Bacteria-mediated lithography of polymer surfaces
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DOI：
10.1021/ja960123c
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发表时间：
1996-09-11
影响因子：
15
通讯作者：
Vulfson, EN
中科院分区：
文献类型：
--
作者：
Aherne, A;Alexander, C;Vulfson, EN
自然界中分子识别的显著例子激发了化学家开始设计和构建合成受体，这些受体可以模仿生物系统与配体的选择性相互作用，结构重组，甚至自组装成超分子结构。1-4实际上，这涉及到制备低分子量的“构建块”，设计用于与模板或通过“互补”表面相互作用。5-19类似地，在模板分子周围的识别位点的组装可以在高度交联的聚合物基质中使用分子印迹技术实现20-24，其中互补功能以可聚合单体的形式引入。然而，到目前为止，在这些快速发展的领域进行的所有工作都涉及相对简单的有机分子。确定是否可行使用大的大分子聚集体甚至整个细胞作为模板来创建互补表面将是非常有趣的。为了实现这样的合成，有必要(i)开发一种能够精确复制模板微生物的大小和形状的方法，（ii）在位点内定位适当的功能，同时确保表面的其余部分保持化学惰性。本通讯描述了一种新的细菌介导的光刻程序，其中细胞实际上充当临时保护组和结构模板，从而使我们能够实现这两个目标。该方案采用一系列化学试剂，最初在温和条件和中性pH下确保生物相容性，如图1所示。在第一步中，我们在搅拌过的细菌悬浮液存在的情况下，将水溶性聚胺和二酸氯在分散的有机相中反应。众所周知，微生物在水层和有机层之间的界面上分裂的趋势，加上二酸氯的存在，能够在细菌细胞壁的亲核基团和聚胺之间形成共价键，确保了模板的定位
The remarkable examples in nature of molecular recognition have inspired chemists to embark on the design and construction of synthetic receptors which can mimic biological systems in terms of selective interactions with ligands, structural reorganization, and even self-assembly into supramolecular architectures. 1-4 In practical terms, this involves the preparation of low molecular weight “building blocks” designed to interact either with a template or with each other via “complementary” surfaces. 5-19 Similarly, the assembly of a recognition site around a template molecule can be achieved within highly crosslinked polymeric matrices using molecular imprinting techniques20-24 where the complementary functionality is introduced in the form of polymerizable monomers. However, all the work carried out within these rapidly developing areas so far has been concerned with relatively simple organic molecules. It would be of great interest to ascertain whether it is feasible to employ large macromolecular aggregates or even whole cells as templates to create complementary surfaces. In order to effect such a synthesis, it is necessary (i) to develop an approach enabling the precise reproduction of the size and shape of the template microorganism and (ii) to position appropriate functionality within the site while at the same time ensuring that the rest of the surface remains chemically inert. This Communication describes a novel bacteria-mediated lithographic procedure, where the cells in effect act as temporary protecting groups and structural templates, thus enabling us to achieve both objectives.The protocol employs a range of chemistries, initially under mild conditions and neutral pH to ensure biocompatibility, as illustrated schematically in Figure 1. In the first step, we reacted a water soluble poly (amine), and a diacid chloride in a dispersed organic phase, in the presence of a stirred suspension of bacteria. The well-known tendency of microorganisms to partition at the interface between aqueous and organic layers, combined with the presence of the diacid chloride, capable of forming covalent bonds between nucleophilic groups in the bacterial cell walls and the poly (amine), ensured that the templates were positioned