The self-assembly of pi-conjugated chromophores directed by biomolecular recognition offers a smart strategy to create bio-synthetic hybrid nanomaterials with emergent properties. Here, we report a novel amphiphilic, cationic naphthalene diimide (NDI) derivative that undergoes supramolecular polymerization upon interaction with anionic glycosaminoglycans (GAGs). Binding of GAGs like heparin to NDIs leads to their supramolecular polymerization in aqueous media. Interestingly, such binding events result in highly emissive fluorescent nanofibers due to the formation of a static excimer. Spectroscopic and microscopic investigations reveal that polyanionic heparin helps to bring the cationic NDIs into close proximity to promote pi-pi stacking and that amphiphilic self-assembly is essential for excimer formation. The heparin binding-induced excimer formation exhibits a clear emission color change from blue to bright green. Furthermore, the NDI selectively binds to sulphated GAGs such as heparin and chondroitin sulphate, but not to carboxylated hyaluronic acid, resulting in a differential fluorescence response. Thus, this study presents a heparin binding-induced supramolecular polymerization of a novel NDI derivative, providing a design strategy for controlling supramolecular order and for creating functional fluorescent nanomaterials for future biosensing and bioimaging applications.
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.
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.
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.
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.
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.
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Sharma, P, López, EFP, Nieto, BC, Calò, A, Ghosh, S, Rodríguez, P, Companyó, X, Limburg, B, Kumar, M, (2026). Selective binding of sulphated glycosaminoglycans induces self-assembly of naphthalene diimide into fluorescent nanofibers Nanoscale 18, 6399-6408 