Systems chemistry: new external stimuli, molecular tools and applications

对人工化学系统的研究有望帮助我们更好地理解细胞生物学中的一些复杂系统效应，并在分子传感、并行化学计算和材料科学中找到实际应用。系统化学是一门年轻的学科，它密切关注发生在复杂化学混合物中的长期被忽视的动态过程。特别令人感兴趣的是，分子网络表现出在宏观和(亚)微观生物系统中普遍存在的“远离平衡”的现象：自我复制、持续的(化学)振荡或对刺激的非线性反应。这一领域的悬而未决的问题包括：如何才能最好地创造不平衡的系统，什么是合适的能源？哪些转变构成了系统化学的工具箱？可能的应用是什么？拟议的研究计划将通过探索动态分子网络扰动的新物理刺激，开发适用于分子传感的可逆共价反应，以及首次从系统化学的角度探讨合成碳同素异构体的化学，来解决所有这些挑战。在子项目1中，超声波和pH振荡器将与动态组合库相结合，以产生非平衡效应，如自分类、化学振荡和在声学驱动的分子马达中的定向平移运动。在子项目2中，将利用正交酯的酸稳定性和三脚架结构来模板化地自组装新的动态大环以及C3对称密码，并探索这种结构在有机分子和金属阳离子传感方面的潜力。在子项目3中，系统化学的范围将扩展到三种不同类型的富勒烯和氧化石墨烯，其可逆的共价官能化可能为在有机电子器件中的应用打开机会。

Research on artificial chemical systems is expected to help us better understand some of the complex system effects in cell biology, and to find practical applications in molecular sensing, parallel chemical computing and material science. Systems chemistry is a young discipline that looks closely at the long-ignored dynamic processes occurring in complex chemical mixtures. Of particular interest are molecular networks that exhibit the ‘far-from-equilibrium’ phenomena ubiquitously found in macroscopic and (sub-)microscopic biological systems: self-replication, sustained (chemical) oscillations or non-linear responses to stimuli. Open questions in this area include: how can out-of-equilibrium systems best be created and what are suitable energy sources? Which transformations comprise the toolbox of systems chemistry? What are possible applications?The proposed research program will address all of these challenges by exploring new physical stimuli for the perturbation of dynamic molecular networks, developing a largely overlooked reversible covalent reaction ideally suited for molecular sensing, and approaching the chemistry of synthetic carbon allotropes, for the first time, from a systems chemistry perspective.In subproject 1, ultrasound and pH-oscillators will be coupled with dynamic combinatorial libraries to produce out-of-equilibrium effects, such as self-sorting, chemical oscillations and directional translational motion in a sonication-driven molecular motor. In subproject 2, the acid-lability and tripodal structure of orthoesters will be exploited for the templated self-assembly of new dynamic macrocycles, as well as C3-symmetric cryptands, and the potential of such architectures for sensing of organic molecules and metal cations will be explored. In subproject 3, the reach of systems chemistry will be extended to three different types of fullerenes and graphene oxide, whose reversible covalent functionalization could open up opportunities for applications in organic electronic devices.