Hydrophobic domain modulation of chemical responsiveness in a bolaamphiphile‐based supramolecular monomer

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

Published: Aug. 22, 2024

Self-immolative chemistries that respond in an irreversible manner to external stimuli are highly attractive permanently degrade filamentous supramolecular biomaterials. Within the monomer, a balance needs be struck between its capacity supramolecularly polymerized and degraded at appropriate rate for given application. Herein, we unravel structure-property-function relationships of library squaramide-based bolaamphiphiles bearing central disulfide-based self-immolative spacer construct polymers responsive chemical aqueous solutions. We examine impact changing alkyl domain length (2 12 methylene units) on formation filaments their degradation response biological antioxidant, glutathione. A minimum octyl is required robustly form can irreversibly through cyclization-elimination reaction triggered by thiol-disulfide exchange. Further increasing peripheral chain decyl increases ordered packing amphiphiles, hindering degradation. This study provides framework design chemically based solutions eventual application as biomedical materials.

Language: Английский

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What Triggers the Dynamic Self-Assembly of Molecules and Materials?

Langmuir, Journal Year: 2023, Volume and Issue: 39(37), P. 12967 - 12974

Published: Sept. 6, 2023

Dynamic self-assembly has emerged as one of the reliable approaches to create complex materials with more life-like functions. In a typical dynamic process, external triggers activate building blocks initiate assembly step form transiently stable higher-order structures. These provide constant supply energy maintain self-assembled states. The withdrawal or consumption trigger deactivates block in aggregates, thereby initiating disassembly step. A precise control over interplay between deterministic and nondeterministic forces is key achieving process. This demands appropriate choice well triggers, which led development wide range self-assembly. Through this Perspective, we intend highlight functional diversities, prospects, challenges associated different classes "triggers" by bringing them under platform. Such treatment will help us identify missing features deduce guideline for ideal triggers. few desirable that should possess, along probable ways achieve them, are discussed, well. summary, Perspective covers many intriguing aspects can be helpful researchers spatiotemporal various interparticle interactions, essential obtaining desired outcome from

Language: Английский

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Functionalization of Supramolecular Polymers by Dynamic Covalent Boroxine Chemistry

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(24)

Published: May 8, 2024

Abstract Molecular scaffolds that enable the combinatorial synthesis of new supramolecular building blocks are promising targets for construction functional molecular systems. Here, we report a scaffold based on boroxine enables formation chiral and ordered 1D polymers, which can be easily functionalized circularly polarized luminescence. The monomers quantitatively synthesized in situ, both bulk solution, from boronic acid precursors cooperatively polymerize into helical aggregates stabilized by threefold hydrogen‐bonding π–π stacking. We then demonstrate amplification asymmetry co‐assembly chiral/achiral co‐condensation classical situ sergeant‐and‐soldiers experiments, respectively, showing fast exchange reactions occurring system. Remarkably, pyrene with results aggregation excimer emission g ‐values order 10 −3 . Yet, electron deficiency boron makes them chemically addressable nucleophiles, but also sensitive to hydrolysis. With this sensitivity mind, provide first insights prospects offered boroxine‐based polymers make addressable, functional, adaptive

Language: Английский

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Growth Mediated Disassembly of Cucurbit[8]uril Cross‐linked Static Cubic Self‐assembly of Silver Nanoparticles

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

Published: July 23, 2024

Abstract Static self‐assembly resides in thermodynamically stable global minima of the energy landscape, whereas dynamic occupies local profile and remains ordered state for a limited time via dissipation to surroundings. This makes spatiotemporal control over assembly disassembly mechanism easily controllable case self‐assembly. However, due higher thermal stability static self‐assembly, it is very challenging perform reverse engineering on these types systems. Herein we report growth reaction‐based reversal silver cubes obtained cucurbit[8]uril (CB[8]) crosslinked nanoparticles (AgNP). The AgNP building units with variable CB[8] surface coverage have been used as seeds onto which deposition gold reaction has performed. supracube structure controlled by formation [AuCl 4 ] − –CB[8] complex successive reduction Au 0 seed. resulting monodispersed isotropic nanoparticles, formed from based cubic after growth, exhibit Au−Ag bimetallic nature. Quenching fluorogenic response hydrophobic dye coumarin‐7, added suggests direct interaction metallic nanoparticle thereby confirms successful mediated

Language: Английский

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