Publications

Metabolism in biological systems involves the continuous formation and breakdown of chemical and structural components, driven by chemical energy. In specific, metabolic processes on cellular membranes result in in situ formation and degradation of the constituent phospholipid molecules, by consuming fuel, to dynamically regulate the properties. Synthetic analogs of such chemically fueled phospholipid vesicles have been challenging. Here we report a bio-inspired approach for the in situ formation of phospholipids, from water soluble precursors, and their fuel driven self-assembly into vesicles. We show that the kinetic competition between anabolic and catabolic-like reactions leads to the formation and enzymatic degradation of the double-tailed, vesicle-forming phospholipid. Spectroscopic and microscopic analysis demonstrate the formation of transient vesicles whose lifetime can be easily tuned from minutes to hours. Importantly, our design results in the formation of uniform sized (65 nm) vesicles simply by mixing the precursors, thus avoiding the traditional complex methods. Finally, our sub-100 nm vesicles are of the right size for application in drug delivery. We have demonstrated that the release kinetics of the incorporated cargo molecules can be dynamically regulated for potential applications in adaptive nanomedicine.

JTD Keywords: Droplets, Mode, Phospholipids, Supramolecular chemistry, Systems chemistry, Transient assembl, Vesicles

Supramolecular systems chemistry has been an area of active research to develop nanomaterials with life-like functions. Progress in systems chemistry relies on our ability to probe the nanostructure formation in solution. Often visualizing the dynamics of nanostructures which transform over time is a formidable challenge. This necessitates a paradigm shift from dry sample imaging towards solution-based techniques. We review the application of state-of-the-art techniques for real-time, in situ visualization of dynamic self-assembly processes. We present how solution-based techniques namely optical super-resolution microscopy, solution-state atomic force microscopy, liquid-phase transmission electron microscopy, molecular dynamics simulations and other emerging techniques are revolutionizing our understanding of active and adaptive nanomaterials with life-like functions. This Review provides the visualization toolbox and futuristic vision to tap the potential of dynamic nanomaterials.© 2022 Wiley-VCH GmbH.

JTD Keywords: electron-microscopy, fluorescence microscopy, in-situ, mechanical-properties, molecular simulations, nanostructures, polymerization, polymers, stimulated-emission, super-resolution microscopy, supramolecular chemistry, systems chemistry, water, Atomic-force microscopy, Liquid tem, Nanostructures, Super-resolution microscopy, Supramolecular chemistry, Systems chemistry

Supramolecular chemistry is the quintessential backbone of all biological processes. It encompasses a wide range from the metabolic network to the self-assembled cytoskeletal network. Combining the chemical diversity with the plethora of functional depth that biological systems possess is a daunting task for synthetic chemists to emulate. The only route for approaching such a challenge lies in understanding the complex and dynamic systems through advanced analytical techniques. The supramolecular complexity that can be successfully generated and analyzed is directly dependent on the analytical treatment of the system parameters. In this review, we illustrate advanced analytical techniques that have been used to investigate various supramolecular systems including complex mixtures, dynamic self-assembly, and functional nanomaterials. The underlying theme of such an overview is not only the exceeding detail with which traditional experiments can be probed but also the fact that complex experiments can now be attempted owing to the analytical techniques that can resolve an ensemble in astounding detail. Furthermore, the review critically analyzes the current state of the art analytical techniques and suggests the direction of future development. Finally, we envision that integrating multiple analytical methods into a common platform will open completely new possibilities for developing functional chemical systems.

JTD Keywords: analytical techniques, dynamic self-assembly, high-speed afm, liquid cell tem, Analytical technique, Analytical techniques, Biological process, Chemical analysis, Chemical diversity, Complex networks, Cytoskeletal network, Dynamic self-assembly, High-speed afm, Hydrogels, In-situ, Liquid cell tem, Metabolic network, Microscopy, Nanoscale, Proteins, Self assembly, Supramolecular chemistry, Supramolecular systems, System chemistry, Systems chemistry