Unraveling the Atomistic Mechanism of Electrostatic Lateral Association of Peptide β‐Sheet Structures and Its Role in Nanofiber Growth and Hydrogelation

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Abstract Guiding molecular assembly of peptides into rationally engineered nanostructures remains a major hurdle against the development functional peptide‐based nanomaterials. Various non‐covalent interactions come play to drive formation and stabilization these assemblies, which electrostatic are key. Here, atomistic mechanisms by contribute toward controlling self‐assembly lateral association ultrashort β‐sheet forming deciphered. Our results show that this is governed charge distribution ionic complementarity, both affecting interaction patterns between charged residues: terminal, core, and/or terminal‐to‐core attraction/repulsion. Controlling enabled fine‐tuning nanofiber morphology for 16 examined peptides, resulting versatile ranging from extended thin fibrils thick bundles twisted helical “braids” short pseudocrystalline nanosheets. This in turn affected physical appearance viscoelasticity formed materials, varying turbid colloidal dispersions viscous solutions soft stiff self‐supportive hydrogels, as revealed oscillatory rheology. Atomistic were confirmed dynamic simulations, validating nanoscopic characterization developed materials. In essence, detailed emphasizing impact complementarity on self‐assembly, nanostructure formation, hydrogelation reported.

Language: Английский

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Influence of chirality and sequence in lysine-rich lipopeptide biosurfactants and micellar model colloid systems

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 8, 2024

Abstract Lipopeptides can self-assemble into diverse nanostructures which be programmed to incorporate peptide sequences achieve a remarkable range of bioactivities. Here, the influence sequence and chirality on micelle structure interactions is investigated in series lipopeptides bearing two lysine or D -lysine residues tyrosine tryptophan residues, attached hexadecyl lipid chain. All molecules micelles above critical concentration (CMC). Small-angle x-ray scattering (SAXS) used probe shape from form factor inter-micellar via analysis factor. The CMC obtained consistently surface tension electrical conductivity measurements. We introduce method obtain zeta potential SAXS good agreement with directly measured values. Atomistic molecular dynamics simulations provide insights packing conformation within lipopeptide constitute model self-assembling colloidal systems biomaterials.

Language: Английский

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Injectable iodine-containing peptide hydrogel for treatment of MRSA infection

Bioactive Materials, Journal Year: 2025, Volume and Issue: 47, P. 198 - 208

Published: Jan. 22, 2025

Language: Английский

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External Stimuli-Driven Catalytic Hydrogels for Biomedical Applications

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review discusses design strategies for external stimuli-driven hydrogels with in situ catalytic processes. It highlights precise control over the properties, elucidating regulatory mechanisms and deepening understanding of applications.

Language: Английский

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Chiroptical hybrid nanomaterials based on metal nanoparticles and biomolecules

Advances in Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 341, P. 103501 - 103501

Published: March 30, 2025

Language: Английский

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Hierarchical chirality conversion switched by biaxial halogen bonding

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Precise control over chirality across hierarchical levels of peptides enriches the toolbox peptide-based chiroptical materials. In this work, we report a controlled conversion from folded molecular to supramolecular chirality, which can be effectively switched by biaxial halogen bonds. Amino acid segments were conjugated bipyridine core as β-turn facilitate formation parallel β-sheet arrays, enables intramolecular transfer appended pyrenes. This allows for efficient excimer emission and boosted circularly polarized luminescence with dissymmetry factor up 10-2. The folding structures are self-assembled into nanohelices where is dominated emerged heterochirality in response solvent medium. introduction hypervalent iodine(iii) species binds peptide via strong I⋯N bonds that transform well-ordered helices amorphous nanoparticles. bonding complexation rearranges assembly extremely high efficacy, suppressing recovering when activities rationally manipulated. work unveils dynamic artificially peptides, will inspire design protocols peptide- or protein-based

Language: Английский

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Metal Ions Trigger the Gelation of Cysteine‐Containing Peptide‐Appended Coordination Cages

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 3, 2024

Abstract We report a series of coordination cages that incorporate peptide chains at their vertices, prepared through subcomponent self‐assembly. Three distinct heterochiral tripeptide subcomponents were incorporated, each exhibiting an L−D−L stereoconfiguration. Through this approach, we and characterized three tetrahedral metal‐peptide thiol methylthio groups. The gelation these was probed the binding additional metal ions, with acting as junctions, owing to presence sulfur atoms on peripheral peptides. Gels obtained bearing cysteine C‐terminus. Our strategy for developing functional metal‐coordinated supramolecular gels modular design may result in development materials useful chemical separations or drug delivery.

Language: Английский

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Self-assembly of Tyrosine-containing Peptides into Injectable Hydrogels with Distinct Nanostructures is Key in Determining Inflammatory Response of Macrophages

Published: March 27, 2024

Self-assembling peptides (SAPs) are fully defined nanobiomaterials offering unprecedented opportunities to control nanostructure and chemical attributes investigate manipulate cellular signals. To the influence of morphological characteristics on inflammatory signalling in native immunity, we designed five beta-sheet SAPs: EFEFKFEFK (EF8), YEFEFKFEFK (YEF8), (EF8Y), (YEF8Y) EYEFKFEFK (EYF8) (F: phenylalanine; E: glutamic acid; K: lysine, Y: tyrosine). The position tyrosine peptide sequence dictated distinct self-assembly into nanostructures, with sequences EF8Y, YEF8Y, EYF8 self-assembling thin nanofibers d≈3.8 ± 0.2 nm, YEF8 rod-like flat ribbons d>20 nm EF8 (control) consisting both types self-assembled nanostructures. These nanostructures induced contrasting response monocytic model THP-1 cells-derived macrophages (MΦs). Presence soluble (at 2 mM) anti-inflammatory polarization towards an M2 state, whereas displayed tendency for inducing pro-inflammatory M1 state. SAPs did not induce our models. results were validated using peripheral blood mononuclear cells (PBMCs)-derived MΦs from human donors, confirming critical role as possible orchestrators repair tissues or inducers respectively. findings will facilitate utilization this family immunomodulatory potentially changing course inflammation during progression various diseases.

Language: Английский

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Rational design of self‐assembling ultrashort peptides for the shape‐ and size‐tunable synthesis of metal nanostructures

Journal of Peptide Science, Journal Year: 2024, Volume and Issue: 31(1)

Published: Aug. 23, 2024

Peptides have attracted great interest as platforms for the design of nanocomposite hydrogels due to their distinct bioactivity, biofunctionality and biocompatibility. Previously, we reported on a family peptides that self‐assembled form stabilised three‐dimensional hydrogel networks, displaying potent antimicrobial activity. In this paper, report use these hydrogelator sequences analogues stabilisers growth controllers synthesise anisotropic gold nanoparticles (AuNPs) different sizes shapes. particular, hollow spherical were obtained HG2.81 ‐AuNPs, whereas hexagonal observed TOH_1 N ‐AuNPs PentaOH in respective networks. The ‐AuNPs' exhibited excellent results with high potency against Staphylococcus aureus Pseudomonas aeruginosa ATCC 27853 negligible cytotoxicity. On other hand, TOH_1N showed no antibacterial activity cytotoxicity, demonstrating versatility peptides. This work gives credence towards development materials further applications such tissue culture technology wound dressing materials.

Language: Английский

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A water playground for peptide re-assembly from fibrils to plates

Journal of Materials Chemistry B, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Short-peptide amyloid assembly and disassembly play crucial roles in various research fields, which range from addressing pathologies that lack therapeutic solutions to the development of innovative soft (bio)materials. Hydrogels short peptides typically show thermo-reversible gel-to-sol transition, whereby fibrils disassemble upon heating, re-assemble cooling down room temperature (rt). Despite ongoing intense studies this area, majority focus on peptide-peptide interaction neglect structuring role water peptide supramolecular behavior. This study describes an unprotected tetrapeptide gelator forms highly stable which, re-organize into plates persist rt. All-atom molecular dynamics (MD) simulations experimental methods reveal as a key player thermodynamics accompany irreversible morphological advance our understanding structures.

Language: Английский

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