Applying Silicon Biotechnology to the Synthesis of Structured Materials

绿色化学的12个原则，由Anastas和Warner于1998年首次提出，为化学家提供了减少化学过程对环境影响的指导方针。 生物技术代表了可用于开发硅化学中的绿色方法的一种途径。 我们建议通过硅基结构材料的合成和研究继续探索硅生物技术。 硅生物技术将应用于两类主要化合物的合成：（i）含胆甾烷的磷脂，和（ii）自我修复，可回收的有机硅聚合物。 ** 我们的初步工作表明，生物催化可用于合成磷脂结构的硅氧烷类似物。 然而，生物相关的磷脂通常需要通过膜的多次挤出循环以获得具有100 nm直径的单层囊泡，硅氧烷磷脂自发地形成具有100-150 nm直径的单层脂质体。 硅生物技术将用于合成含硅脂质结构库。 这个脂质库将包括对脂质尾部和头部基团的修饰，这将使我们能够更好地了解这些胆甾烷-脂质分子如何相互作用以及为什么它们会自发地自组装。 用荧光示踪剂修饰脂质尾部将使研究这些膜系统的流动性成为可能。有机硅聚合物在我们的世界中无处不在，应用于润滑剂，粘合剂，绝缘体，个人护理产品等。然而，用于此类应用的有机硅弹性体的一个基本限制是它们易受机械损伤，这可能影响材料的使用寿命，并且这些材料通常难以回收。 根据绿色化学的原则，我们建议将硅生物技术应用于自修复、可回收的有机硅的合成。 基于我们现有的专业知识，将探索通过Diels-Alder加合物交联的有机硅聚合物。 将使用化学酶法合成线性、环状和树枝状硅酮。 将研究这些材料从机械损伤中愈合的能力以及它们的物理机械性能。 ** 硅生物技术将在含硅磷脂和自我修复、可回收的有机硅聚合物等结构材料的合成中发挥不可或缺的作用。 该计划将使我们能够进一步发展我们对硅化学中生物催化反应的理解，同时探索有趣的聚合物和生物相关的含硅材料。

The 12 Principles of Green Chemistry, first proposed in 1998 by Anastas and Warner, provide chemists with guidelines for lessening the environmental impact of chemical processes. Biotechnology represents one route that can be utilized to develop green methodologies in silicon chemistry. We propose to continue our exploration of silicon biotechnology through the synthesis and study of silicon-based structured materials. Silicon biotechnology will be applied to the synthesis of two principle classes of compounds: (i) siloxane-containing phospholipids, and (ii) self-healing, recyclable silicone polymers. ******Our preliminary work has demonstrated that biocatalysis can be utilized in the synthesis of siloxane analogues of phospholipid structures. Whereas biologically relevant phospholipids typically require multiple extrusion cycles through a membrane in order to achieve unilamellar vesicles with a 100 nm diameter, siloxane phospholipids spontaneously form unilamellar liposomes with a diameter of 100-150 nm. Silicon biotechnology will be used to synthesize a library of silicon-containing lipid structures. This library of lipids will include modifications to the lipids tails and the head group, which will allow us to better understand how these siloxane-lipid molecules interact and why they spontaneously self-assemble. Modification of the lipid tails with a fluorescent tracer will make it possible to study the fluidity of these membrane systems.******Silicone polymers are ubiquitous in our world, found in applications such as lubricants, adhesives, insulators, personal care products, etc. However, one of the fundamental limitations of silicone elastomers used in such applications is that they are subject to mechanical damage, which can impinge upon the material's useful lifetime, and these materials are often difficult to recycle. In keeping with the Principles of Green Chemistry, we propose to apply silicon biotechnology to the synthesis of self-healing, recyclable silicones. Building upon our existing expertise, silicone polymers cross-linked via a Diels-Alder adduct will be explored. Linear, cyclic, and dendritic silicone will be synthesized using a chemoenzymatic approach. The capacity for these materials to heal from mechanical damage as well as their physicomechanical properties will be studied. ******Silicon biotechnology will play an integral role in the synthesis of structured materials such as silicon-containing phosphlipids and self-healing, recyclable silicone polymers. This programme will permit us to further develop our understanding of biocatalytic reactions in silicon chemistry, while concomitantly exploring interesting polymeric and biologically related silicon-containing materials.