Discrete Actuation of Water-Responsive Crystalline Metal-Peptide Frameworks.

Engineering guest-responsive materials capable of controlled and precise sorption behavior and structural deformation in response to external stimuli is imperative for various applications. However, existing systems often exhibit complex, unpredictable dynamics, posing challenges for efficient control and utilization. Here, we design crystalline metal-peptide frameworks with tunable water-responsive (WR) dynamics by assembling glycine-threonine (Gly-Thr, GT) or glycine-serine (Gly-Ser, GS) peptides with zinc (Zn) ions, achieving either continuous or discrete threshold water-sorption-dependent phase transitions.

Controlling Amyloid Assembly Dynamics Using Spin Interfaces.

Protein aggregation into amyloid fibrils is central to numerous diseases, yet the role of electron spin interactions during nucleation and self-assembly remains unexplored. We investigated amyloid formation of A-β(1-42) polypeptide, implicated in Alzheimer's disease, and its smaller recognition motifs on ferromagnetic substrates. We observed a strong dependence of fibril formation dynamics on the substrate's magnetization orientation using electron and fluorescence microscopy.

Effect of solvent-induced packing transitions on N-capped diphenylalanine peptide crystal growth.

Self-assembled supramolecular materials have gained extensive interest due to their ability to form structures with diverse physical, chemical, and biological properties. These characteristics arise from the precise arrangement of building blocks at the nanoscale. There is an unmet need to efficiently manipulate crystalline materials' solid-state packing and monitor the effect on growth at a single crystal level.

Multienzyme (3-in-1)-Mimicking a Single Nucleobase-Derived Bionanozyme for Versatile Environmental and Biomedical Applications.

The quest for efficient, robust, and sustainable solutions in environmental remediation and advanced biosensing has catalyzed significant interest in biomimetic enzymology. Here, a new Bionanozyme, synthesized from a single nucleobase-adenine (A)-coordinated with copper (Cu) in a 2D crystalline structure (A-Cu), is presented. This state-of-the-art A-Cu Bionanozyme, inspired by natural redox enzymes (Laccase (LAC), Catechol oxidase (CO), and Peroxidase (POD)), is synthesized via simple and scalable, green methods including solvent-free co-grinding and natural aqueous evaporation process.

On-Chip De Novo Production of mRNA Vaccine in Lipid Nanoparticles.

RNA-based therapeutics have revolutionized precision medicine due to their unprecedented potency, specificity, and adaptability. However, the inherent limited stability of RNA, including mRNA used in vaccines, is a major obstacle to the full realization of their potential. This instability, coupled with the centralized nature of vaccine production, currently limits the generation of RNA therapeutics at the point of care, which will otherwise fully harness the potential of these agents.

Bioinspired supramolecular fibrillization enables stretchable and biodegradable piezoelectric bioelectronics.

Bioinspired piezoelectricity is extensively explored for diverse bio-machine interface and biomedical engineering applications. Nevertheless, state-of-the-art bio-piezoelectricity mainly focuses on crystallization. Yet, crystalized structures exhibit several shortcomings, including limited biocompatibility or biodegradability along with intrinsic non-stretchability.

Self-Assembly Pathway Influence on Dehydropeptide-Based Gel Properties and Drug Release.

Low-molecular-weight peptide-based hydrogels formed through self-assembly have emerged as promising candidates for biomedical applications. While the self-assembly process is known to affect the network morphology, its impact on mechanical properties and drug delivery remains poorly understood. In this work, it is explored how different gelation conditions influence the morphology, properties, and drug release profiles of dehydropeptide-based gels.

Crystallization of L-Cysteine in Heavy Water Induces Intrinsic Fluorescence.

Developing noninvasive techniques that can probe how solvents modulate the nucleation pathways of bioorganic molecules in solution remains an active and open area of research. Herein, we investigate the crystallization of the amino acid L-Cysteine and show that both the structure of the crystal and its intrinsic fluorescence can be drastically altered by the solvent. Crystals formed in heavy water exhibit markedly different intermolecular packing as well as strikingly different monomer conformations compared to those in light water.

Correction: Preventing biofilm formation and eradicating pathogenic bacteria by Zn doped histidine derived carbon quantum dots.

Correction for 'Preventing biofilm formation and eradicating pathogenic bacteria by Zn doped histidine derived carbon quantum dots' by Vijay Bhooshan Kumar , , 2024, , 2855-2868, https://doi.org/10.1039/D3TB02488A.

Amyloid inspired single amino acid (phenylalanine)-based supramolecular functional assemblies: from disease to device applications.

In the evolving landscape of biomolecular supramolecular chemistry, recent studies on phenylalanine (Phe) have revealed important insights into the versatile nature of this essential aromatic amino acid. Phe can spontaneously self-assemble into fibrils with amyloid-like properties linked to the neurological disorder phenylketonuria (PKU). Apart from its pathological implications, Phe also displays complex phase behavior and can undergo structural changes in response to external stimuli.

Interplay between Antimicrobial Peptides and Amyloid Proteins in Host Defense and Disease Modulation.

The biological properties of antimicrobial peptides (AMPs) and amyloid proteins and their cross-talks have gained increasing attention due to their potential implications in both host defense mechanisms and amyloid-related diseases. However, complex interactions, molecular mechanisms, and physiological applications are not fully understood. The interplay between antimicrobial peptides and amyloid proteins is crucial for uncovering new insights into immune defense and disease mechanisms, bridging critical gaps in understanding infectious and neurodegenerative diseases.

Phenylalanine-embedded carbazole-based fluorescent 'turn-off' chemosensor for the detection of metal ions.

Fluorescent chemosensors are highly important for various applications including medical diagnostics, environmental monitoring, and industrial processing. Significant advancements have been made to produce sensors capable of detecting biologically and environmentally relevant ions. Specifically, carbazole-derived fluorophores are chemically stable agents with the ability to detect anions, cations, and small bioorganic molecules.

A rapid in vivo pipeline to identify small molecule inhibitors of amyloid aggregation.

Amyloids are associated with over 50 human diseases and have inspired significant effort to identify small molecule remedies. Here, we present an in vivo platform that efficiently yields small molecule inhibitors of amyloid formation. We previously identified small molecules that kill the nematode C.

Amylum forms typical self-assembled amyloid fibrils.

Amyloid fibril formation is a central biochemical process in pathology and physiology. Over decades, substantial advances were made in elucidating the mechanisms of amyloidogenesis, its links to disease, and the production of functional supramolecular structures. While the term "amyloid" denotes starch-like features of these assemblies, no evidence of amyloidogenic behavior of polysaccharides has been so far reported.

The Dimensionality of Hydrogen Bond Networks Induces Diverse Physical Properties of Peptide Crystals.

Short peptides are attractive building blocks for the fabrication of self-assembled materials with significant biological, chemical, and physical properties. The microscopic and macroscopic properties of assemblies are usually closely related to the dimensionality of formed hydrogen bond networks. Here, two completely different supramolecular architectures connected by distinct hydrogen bond networks were obtained by simply adding a hydroxyl group to switch from cyclo-tryptophan-alanine (cyclo-WA) to cyclo-tryptophan-serine (cyclo-WS).

A broad-spectrum antibacterial hydrogel based on the synergistic action of Fmoc-phenylalanine and Fmoc-lysine in a co-assembled state.

Multicomponent biomolecular self-assembly is fundamental for accomplishing complex functionalities of biosystems. Self-assembling peptides, amino acids, and their conjugates serve as a versatile platform for developing biomaterials. However, the co-assembly of multiple building blocks showing synergistic interplay between individual components and producing biomaterials with emergent functional attributes is much less explored.

A self-healing multispectral transparent adhesive peptide glass.

Despite its disordered liquid-like structure, glass exhibits solid-like mechanical properties. The formation of glassy material occurs by vitrification, preventing crystallization and promoting an amorphous structure. Glass is fundamental in diverse fields of materials science, owing to its unique optical, chemical and mechanical properties as well as durability, versatility and environmental sustainability.

Characterization of amyloid-like metal-amino acid assemblies with remarkable catalytic activity.

While enzymes are potentially useful in various applications, their limited operational stability and production costs have led to an extensive search for stable catalytic agents that will retain the efficiency, specificity, and environmental-friendliness of natural enzymes. Despite extensive efforts, there is still an unmet need for improved enzyme mimics and novel concepts to discover and optimize such agents. Inspired by the catalytic activity of amyloids and the formation of amyloid-like assemblies by metabolites, our group pioneered the development of novel metabolite-metal co-assemblies (bio-nanozymes) that produce nanomaterials mimicking the catalytic function of common metalloenzymes that are being used for various technological applications.

Ring-opening polymerization of lactide catalyzed using metal-coordinated enzyme-like amino acid assemblies.

Polylactide (PLA), a biocompatible and biodegradable polymer, is widely used in diverse biomedical applications. However, the industry standard for converting lactide into PLA involves toxic tin (Sn)-based catalysts. To mitigate the use of these harmful catalysts, other environmentally benign metal-containing agents for efficient lactide polymerization have been studied, but these alternatives are hindered by complex synthesis processes, reactivity issues, and selectivity limitations.

Co-Assembly of Cancer Drugs with Cyclo-HH Peptides: Insights from Simulations and Experiments.

Peptide-based nanomaterials can serve as promising drug delivery agents, facilitating the release of active pharmaceutical ingredients while reducing the risk of adverse reactions. We previously demonstrated that Cyclo-Histidine-Histidine (Cyclo-HH), co-assembled with cancer drug Epirubicin, zinc, and nitrate ions, can constitute an attractive drug delivery system, combining drug self-encapsulation, enhanced fluorescence, and the ability to transport the drug into cells. Here, we investigated both computationally and experimentally whether Cyclo-HH could co-assemble, in the presence of zinc and nitrate ions, with other cancer drugs with different physicochemical properties.

Peptide hydrogen-bonded organic frameworks.

Hydrogen-bonded porous frameworks (HPFs) are versatile porous crystalline frameworks with diverse applications. However, designing chiral assemblies or biocompatible materials poses significant challenges. Peptide-based hydrogen-bonded porous frameworks (P-HPFs) are an exciting alternative to conventional HPFs due to their intrinsic chirality, tunability, biocompatibility, and structural diversity.

Ordered planar plating/stripping enables deep cycling zinc metal batteries.

Metal anodes are emerging as culminating solutions for the development of energy-dense batteries in either aprotic, aqueous, or solid battery configurations. However, unlike traditional intercalation electrodes, the low utilization of "hostless" metal anodes due to the intrinsically disordered plating/stripping impedes their practical applications. Herein, we report ordered planar plating/stripping in a bulk zinc (Zn) anode to achieve an extremely high depth of discharge exceeding 90% with negligible thickness fluctuation and long-term stable cycling.

Targeting phenylalanine assemblies as a prospective disease-modifying therapy for phenylketonuria.

Phenylketonuria is characterized by the accumulation of phenylalanine, resulting in severe cognitive and neurological disorders if not treated by a remarkably strict diet. There are two approved drugs today, yet both provide only a partial solution. We have previously demonstrated the formation of amyloid-like toxic assemblies by aggregation of phenylalanine, suggesting a new therapeutic target to be further pursued.