Multiple‐State Control over Supramolecular Chirality through Dynamic Chemistry Mediated Molecular Engineering

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 17, 2024

Abstract Dynamic chemistry utilizing both covalent and noncovalent bonds provides valid protocols in manipulating properties of self‐assemblies functions. Here we employ dynamic to realize multiple‐route control over supramolecular chirality up five states. N‐protected fluorinated phenylalanine the carboxylate state self‐assembled into achiral nanoparticles ascribed amphiphilicity. Protonation promoted one‐dimensional growth helices with shrunk hydrophilicity, which presence disulfide pyridine undergo inversion by hydrogen bonding‐directed coassembly. Further interacting water‐soluble reductant cleavages bond initiate rearrangement coassemblies a as well. Finally, tuning pH environments, aromatic nucleophilic substitution reaction between reduced products perfluorinated occurs, giving distinct chiral nanoarchitectures emerged luminescence circularly polarized luminescence. We thus realized particular five‐state combining at one compound, greatly enriches toolbox fabricating responsive chiroptical materials.

Language: Английский

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Protein‐Inspired Polymers with Tunable Microphase Structures toward Autonomous Self‐Healing in Aqueous Environments

Advanced Materials Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract The self‐healing of polymer materials in aqueous environments remains a significant challenge. Herein, protein‐inspired strategy for hydrophobic/hydrophilic‐induced microphase separation is proposed to construct polymers an environment. During self‐healing, the hydrophobic polydimethylsiloxane microphases damaged region reassociate with each other owing presence dynamic interactions underwater. In addition, hydrophilic carboxyl groups diffuse and penetrate form hydrogen bonds. It found that structure efficiency can be adjusted by regulating hydrophobic/hydrophilic components. efficiencies as‐synthesized deionized water seawater reach 99.1 98.7%, respectively. molecular structures are characterized using Fourier‐transform infrared spectroscopy ultraviolet‐visible while aggregated examined small angle X‐ray scattering atomic force microscopy (AFM). This design strategy, inspired biological sciences, will expected extend application range synthetic intrinsic polymers, especially environments.

Language: Английский

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Supramolecular Gelation Based on Native Amino Acid Tyrosine and Its Charge-Transfer Complex Formation

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

Published: Jan. 15, 2025

Self-assembly of amino acids and short-peptide derivatives attracted significant curiosity worldwide due to their unique self-assembly process wide variety applications. Amino acid is considered one the important synthons in supramolecular chemistry. processes applications unfunctionalized native have been less reported literature. In this article, we are first-time reporting tyrosine (Tyr), an aromatic acid, dimethyl sulfoxide (DMSO) solvent. Most studies related Tyr were different aqueous solutions. our work, studied several common organic solvents found that could self-assemble into a gel The was investigated by techniques, such as UV-vis, fluorescence, FTIR, NMR spectroscopy. Morphological features on nanoscale through scanning electron microscopy (SEM). SEM images indicated formation nanofibrils with high aspect ratios. property rheological experiments. Computational study DMSO medium suggested noncovalent interactions like hydrogen bonding π-π stacking among molecules played prominent role. Finally, charge-transfer complex ability electron-rich electron-deficient 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) studied. presence DDQ formation, converted reddish color solution, fibrillar morphologies collapsed.

Language: Английский

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Chiral Bimetallic Pt@Au Octapods with Spiral Four‐Petal Flower‐Like Symmetric Configuration as Sensitive SERS Probes

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract Here, we synthesized chiral bimetallic Pt@Au octapods by using l / d ‐cysteine–threonine (CT) dipeptide as ligands. These had a distinct spiral four‐petal flower‐like symmetric configuration with twisted concave morphology on each facet. The structure of the facilitated intraparticle coupling, resulting in highly concentrated electric fields within regions, thus creating “hot spots” that produced potent surface‐enhanced Raman scattering (SERS) effect. ‐Pt@Au showed nearly twofold stronger SERS response to Aβ40 and Aβ42 monomers fibrils than octapods. different association constants arose from unique recognition capabilities CT ligands surfaces octapods, which allowed them form specific hydrogen bonds fibrils, producing significant differences their spectra. data clinical cerebrospinal fluid (CSF) samples quantitative analysis Aβ42/Aβ40 ratio spectroscopy can be used an effective biomarker for early diagnosis Alzheimer's disease (AD), cut‐off value 0.085. Our results pave way use nanomaterials strong optical activities development testing instruments biomedical applications.

Language: Английский

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Chiral helical peptide nanomaterials: Construction strategies and applications

Nano Today, Journal Year: 2025, Volume and Issue: 62, P. 102703 - 102703

Published: March 13, 2025

Language: Английский

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Pathway Complexity of Kinetically Trapped Dipeptide‐Based Metastable State: Supramolecular Structural Transformation and Helicity Tuning

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

Published: April 14, 2025

Abstract Understanding the complexity of nanostructures involved during supramolecular polymerization process can be achieved by kinetic control rather than thermodynamic stability. Study on pathway and associated will provide precise over materials' properties. This work illustrates structural transformation a naphthalimide‐(NMI)‐conjugated dipeptide from monomer to thermodynamically stable aggregated state in binary mixed solvent system (DMSO water). The self‐assembly propensity modulated changing ratio water, which offers an effective approach stability on‐pathway gel before reaching its crystalline precipitate state. An in‐depth spectroscopic microscopic investigation suggested that initiated formation tiny particles, further nucleated form helical nanofibrilar assembly. At higher water percentages, showed transient behavior proceeded toward However, at lower percentage, is kinetically trapped Here, helicity nanofibers altering percentage solvent. self‐assembled completely thermoreversible retain chiral memory even after complete dissolution respective composition.

Language: Английский

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Probing Peptide Assembly and Interaction via High-Resolution Imaging Techniques: A Mini Review

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(9), P. 3998 - 3998

Published: April 23, 2025

Peptide molecules, as fundamental structural units in biological systems, play pivotal roles diverse processes and have garnered substantial attention biomolecular self-assembly research. Their simplicity high design flexibility make peptides key players the development of novel biomaterials. High-resolution imaging techniques provided profound insights into peptide assembly. Recently, cutting-edge technologies, such super-resolution microscopy (SRM) with unparalleled spatiotemporal resolution, has further advanced assembly These advancements enable both mechanistic exploration pathways rational peptide-based functional materials. In this mini review, we systematically examine diversity assemblies, including micelles, tubes, particles, fibers hydrogel, investigated by various high-resolution techniques, a focus on their characterization dynamic process. We also summarize interaction networks assemblies proteins, polymers microbes, providing insight interactions between other molecules. Furthermore, emphasize transformative role addressing long-standing challenges nanotechnology. anticipate that review will accelerate advancement characterization, thereby fostering creation next-generation

Language: Английский

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Multiple‐State Control over Supramolecular Chirality through Dynamic Chemistry Mediated Molecular Engineering

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 17, 2024

Abstract Dynamic chemistry utilizing both covalent and noncovalent bonds provides valid protocols in manipulating properties of self‐assemblies functions. Here we employ dynamic to realize multiple‐route control over supramolecular chirality up five states. N‐protected fluorinated phenylalanine the carboxylate state self‐assembled into achiral nanoparticles ascribed amphiphilicity. Protonation promoted one‐dimensional growth helices with shrunk hydrophilicity, which presence disulfide pyridine undergo inversion by hydrogen bonding‐directed coassembly. Further interacting water‐soluble reductant cleavages bond initiate rearrangement coassemblies a as well. Finally, tuning pH environments, aromatic nucleophilic substitution reaction between reduced products perfluorinated occurs, giving distinct chiral nanoarchitectures emerged luminescence circularly polarized luminescence. We thus realized particular five‐state combining at one compound, greatly enriches toolbox fabricating responsive chiroptical materials.

Language: Английский

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Odd‐Even Law Mediated Supramolecular Chirality of Luminescent Dipeptides for Chiroptical Energy Transfer

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Abstract Inherent luminescent short peptides essentially provide opportunities to rationally manipulate supramolecular chirality and chiral luminescence. Herein, a facile protocol construct series of naphthalimide‐appended dipeptides is reported that show ultrasound wave‐activated regulated by odd‐even law. Naphthalimide luminophores are conjugated the dipeptide skeleton with variable alkyl spacers. The presence tyrosine interferes kinetic aggregation into achiral nanoparticles without transfer scale. However, treatment initiates nanoparticle‐to‐helix transition accompanied appeared optics, including Cotton effect circularly polarized luminescence (CPL). parameters, handedness helices chiroptical behaviors, follow law spacers in bearing non‐substituted naphthalimides. amine‐substitution boosted quantum yields whereas no effect. two types constituted ideal energy pairs enable efficient as well transportation containing substituted This work sheds light on construction applications precise control over

Language: Английский

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Design and Applications of Supramolecular Peptide Hydrogel as Artificial Extracellular Matrix

Biomacromolecules, Journal Year: 2024, Volume and Issue: 25(11), P. 6967 - 6986

Published: Oct. 17, 2024

Supramolecular peptide hydrogels (SPHs) consist of peptides containing hydrogelators and functional epitopes, which can first self-assemble into nanofibers then physically entangle together to form dynamic three-dimensional networks. Their porous structures, excellent bioactivity, high dynamicity, similar an extracellular matrix (ECM), have great potential in artificial ECM. The properties the hydrogel are largely dependent on peptides. noncovalent interactions among drive formation assemblies further transition hydrogels, while bioactive epitopes modulate cell-cell cell-ECM interactions. Therefore, SPHs support cell growth, making them ideal biomaterials for ECM mimics. This Review outlines classical molecular design from summarizes recent advancements as ECMs nervous system repair, wound healing, bone cartilage regeneration, organoid culture. emerging SPH platform could provide alternative strategy developing more effective tissue engineering.

Language: Английский

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