Staff member

Membraneless organelles, also known as biomolecular condensates, lack a surrounding membrane and are formed through liquid-liquid phase separation (LLPS). This process enhances reaction efficiency by compartmentalizing and concentrating reactants. Coacervates, a class of condensates, provide promising synthetic alternatives for improving enzymatic reactions. This review examines how LLPS enhances reaction efficiency in both natural and artificial systems, explores the design principles of coacervate-based artificial organelles employed in (bio)catalysis, and discusses challenges and future directions for leveraging LLPS in catalysis.

JTD Keywords: Acid, Activation, Catalysis, Coacervates, Compartmentalization, Droplets, In-vitro, Liquid-liquid phase separation, Membraneless organelles, Microdroplets, Nitric-oxide, Origins, Rna catalysis, Signaling molecules, Transition

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

Chirality is one of the hallmarks of biomolecules. Herein, we utilize heparin, a chiral biomolecule and potent drug, to induce chiral organization into the assembly of an achiral molecule. Polyanionic heparin binds with a dicationic perylenediimide derivative to induce supramolecular helical organization in aqueous medium as well as in a highly competitive cell culture medium. Heparin, an anionic chiral biomolecule, binds to cationic achiral perylenediimide derivative to induce supramolecular helicity, forming chiral nanostructures in both aqueous and cell culture medium.

JTD Keywords: Circularly-polarized luminescence, Dichroism, Nanotubes, Polymers, Stack

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

Peptide-based supramolecular systems chemistry seeks to mimic the ability of life forms to use conserved sets of building blocks and chemical reactions to achieve a bewildering array of functions. Building on the design principles for short peptide-based nanomaterials with properties, such as self-assembly, recognition, catalysis, and actuation, are increasingly available. Peptide-based supramolecular systems chemistry is starting to address the far greater challenge of systems-level design to access complex functions that emerge when multiple reactions and interactions are coordinated and integrated. We discuss key features relevant to systems-level design, including regulating supramolecular order and disorder, development of active and adaptive systems by considering kinetic and thermodynamic design aspects and combinatorial dynamic covalent and noncovalent interactions. Finally, we discuss how structural and dynamic design concepts, including preorganization and induced fit, are critical to the ability to develop adaptive materials with adaptive and tunable photonic, electronic, and catalytic properties. Finally, we highlight examples where multiple features are combined, resulting in chemical systems and materials that display adaptive properties that cannot be achieved without this level of integration.

JTD Keywords: aromatic peptide, biological-properties, chemical control, conformational-analysis, electronic transport, mechanical-properties, perylene bisimide, pro-hyp sequences, residues determine, Self-assembling peptide