Chemo-Mechanical and Chemo-Structural pH-Feedback Mechanisms to Program Transient and Autonomous Self-Assembling Systems

在之前的资助阶段，我们设想了在均匀溶液中具有瞬态ph状态的ph反馈系统，并将它们与各种ph可切换的自组装相结合，以在自主系统中对其进行自我调节寿命的编程，本提案针对主动反馈机制和自主，化学燃料，非平衡软物质和自组装系统的设计方面的下一步。因此，该建议超越了均匀溶液中的化学反馈，旨在开发和定量理解可推广的，自我调节的，耦合的化学- x ph反馈机制：(i)化学-机械ph反馈系统基于ph调节酶（具有ph依赖的活性谱），嵌入ph响应核-壳胶体中，具有ph依赖的门控效应（底物扩散），以自我调节酶活性。（ii）化学结构ph反馈系统是基于嵌入在共组装核壳胶体中的ph调节酶级联，具有ph依赖的共组装行为，形成的共组装编码其自身的破坏。这将产生新的系统特征，包括(a)具有可控滞后时间和寿命的瞬态ph曲线，(b)可以通过为嵌入的酶提供真正的休眠区域来重新激活的ph曲线，以及(c)通过控制滞后效应、反应/扩散时间尺度的同步，以及由化学-机械反馈施加的暂时控制的自门效应以及临时协调的自调节化学-结构反馈来振荡系统。这些使能的概念允许自主动态材料系统的进步，产生自我调节和时间编程记忆功能。我们的目标是研究新型自擦二肽水凝胶的这种行为，并展示它们在微流控电路中用于流体引导的应用。具体目标是寻找溶胶-凝胶-溶胶系统中延迟和寿命时间正交规划的途径，并利用凝胶化发生前的受控滞后时间，允许前体在分支通道网络中的受控分布，以模拟复杂血管网络中的血流阻塞。

Building on the preceding funding phase, where we conceived pH-feedback systems with transient pH-states in homogeneous solution, and coupled them to a diverse range of pH-switchable self-assemblies to program them with self-regulating lifetimes in autonomous systems, this proposal targets the next steps in terms of active feedback mechanisms and in the design of autonomous, chemically fuelled, non-equilibrium soft matter and self-assembly systems. This proposal hence goes beyond chemical feedback in homogeneous solution and aims to develop and quantitatively understand generalizable, self-regulating, coupled chemo-X pH-feedback mechanisms:(i) chemo-mechanical pH-feedback systems are based on pH-modulating enzymes (with pH-dependent activity profile) as embedded in pH-responsive core-shell colloids with pH-dependent gating effects (substrat diffusion) to self-regulate the enzymatic activity. (ii) chemo-structural pH-feedback system are based on pH-modulating enzyme cascades as embedded in co-assembling core-shell colloids, featuring pH-dependent co-assembly behavior, and in which a formed co-assembly encodes its own destruction. This will give rise to new systems features, including (a) transient pH-profiles with controlled lag times and lifetimes, (b) pH-profiles that can be reactivated by providing truly dormant areas to the embedded enzymes, and (c) oscillating systems by controlled synchronization of hysteresis effects, reaction/diffusion timescales, and temporally controlled self-gating effects imposed by chemo-mechanical feedback as well as temporally orchestrated self-regulating chemo-structural feedback.These enabling concepts allow advancements toward autonomously dynamic material systems, spawning self-regulation and time-programmed memory functions. We aim to investigate this behavior for new types of self-erasing dipeptide hydrogels and showcase their use for fluidic guidance in microfluidic circuits. Particular aims are to find pathways towards an orthogonal programming of lag and life times in sol-gel-sol systems, and to exploit controlled lag times before gelation occurs to allow controlled distribution of precursors into branching channel networks to mimic blood flow blocking in complex vascular networks.