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The tunability of chromatic phases adapted by chromogenic polymers such as polydiacetylene (PDA) is key to their utility for robust sensing applications. Here, we investigated the influence of charged peptide interactions on the structure-dependent thermochromicity of amphiphilic PDAs. Solid-state NMR and circular dichroism analyses show that our oppositely charged peptide-PDA samples have distinct degrees of structural order, with the coassembled sample being in between the ß-sheet-like positive peptide-PDA and the relatively disordered negative peptide-PDA. All solutions exhibit thermochromicity between 20 and 80 °C, whereby the hysteresis of the blue, planar phase is much larger than that of the red, twisted phase. Resonance Raman spectroscopy of films demonstrates that only coassemblies with electrostatic complementarity stabilize coexisting blue and red PDA phases. This work reveals the nature of the structural changes responsible for the thermally responsive chromatic transitions of biomolecule-functionalized polymeric materials and how this process can be directed by sequence-dictated electrostatic interactions.
Assuntos
Nanoestruturas , Poli-Inos , Poli-Inos/química , Polímero Poliacetilênico , Polímeros/química , PeptídeosRESUMO
The deployment of organic molecules in high-performance devices strongly relies on the formation of well-ordered domains, which is often complicated by the dynamic and sensitive nature of supramolecular interactions. Here, we engineered the assembly of water-processable, optoelectronic π-conjugated peptides into well-defined organic-inorganic heterointerfaced assemblies by leveraging the long-range anisotropic ordering of 1D van der Waals (vdW) crystals composed of subnanometer-thick transition metal sulfide chains (MS3; M = Nb, Ta) as assembly templates. We found that the monomers can readily form 1D supramolecular assemblies onto the underlying crystal surface, owing to the structural correspondence between the π-π interactions of the quaterthiophene (4T)-based peptide units (DDD-4T) and sulfur atom ordering along the NbS3 (100) surface. The heterointerfaced assemblies exhibited substantially red-shifted photoluminescence and enhanced visible-range photocurrent generation compared to solution-assembled films. Our results underscore the role of lattice matching in forming ordered supramolecular assemblies, offering an emergent approach to assembling organic building blocks endowed with improved physical properties.
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The conduction efficiency of ions in excitable tissues and of charged species in organic conjugated materials both benefit from having ordered domains and anisotropic pathways. In this study, a photocurrent-generating cardiac biointerface is presented, particularly for investigating the sensitivity of cardiomyocytes to geometrically comply to biomacromolecular cues differentially assembled on a conductive nanogrooved substrate. Through a polymeric surface-templated approach, photoconductive substrates with symmetric peptide-quaterthiophene (4T)-peptide units assembled as 1D nanostructures on nanoimprinted polyalkylthiophene (P3HT) surface are developed. The 4T-based peptides studied here can form 1D nanostructures on prepatterned polyalkylthiophene substrates, as directed by hydrogen bonding, aromatic interactions between 4T and P3HT, and physical confinement on the nanogrooves. It is observed that smaller 4T-peptide units that can achieve a higher degree of assembly order within the polymeric templates serve as a more efficient driver of cardiac cytoskeletal anisotropy than merely presenting aligned -RGD bioadhesive epitopes on a nanotopographic surface. These results unravel some insights on how cardiomyocytes perceive submicrometer dimensionality, local molecular order, and characteristics of surface cues in their immediate environment. Overall, the work offers a cardiac patterning platform that presents the possibility of a gene modification-free cardiac photostimulation approach while controlling the conduction directionality of the biotic and abiotic components.
Assuntos
Miócitos Cardíacos , Peptídeos , Miócitos Cardíacos/citologia , Miócitos Cardíacos/metabolismo , Peptídeos/química , Anisotropia , Animais , Nanoestruturas/química , Tiofenos/química , Propriedades de SuperfícieRESUMO
Multi-scale organization of molecular and living components is one of the most critical parameters that regulate charge transport in electroactive systems-whether abiotic, biotic, or hybrid interfaces. In this article, an overview of the current state-of-the-art for controlling molecular order, nanoscale assembly, microstructure domains, and macroscale architectures of electroactive organic interfaces used for biomedical applications is provided. Discussed herein are the leading strategies and challenges to date for engineering the multi-scale organization of electroactive organic materials, including biomolecule-based materials, synthetic conjugated molecules, polymers, and their biohybrid analogs. Importantly, this review provides a unique discussion on how the dependence of conduction phenomena on structural organization is observed for electroactive organic materials, as well as for their living counterparts in electrogenic tissues and biotic-abiotic interfaces. Expansion of fabrication capabilities that enable higher resolution and throughput for the engineering of ordered, patterned, and architecture electroactive systems will significantly impact the future of bioelectronic technologies for medical devices, bioinspired harvesting platforms, and in vitro models of electroactive tissues. In summary, this article presents how ordering at multiple scales is important for modulating transport in both the electroactive organic, abiotic, and living components of bioelectronic systems.
Assuntos
Engenharia , Polímeros , Polímeros/químicaRESUMO
Precision control via molecular structure over adaptive conjugated polymer properties in aqueous environments is critical for realizing their biomedical applications. Here, we unravel the dependence of amphiphilic peptide-polydiacetylene (PDA) conjugate properties on the characteristic steric and hydrophobic contributions within peptide segments that serve as a biomimetic template for diacetylene polymerization in water. We investigated the functional impacts of molecular volume and polarity changes brought by dipeptide substitution domains on the following peptide-PDA material properties at multiple length scales: supramolecular assembly behavior, chain conformation-dependent photophysical properties, cell-material interfacing, and for the first time, bulk electrical properties of their films processed in water. A library of peptide-PDAs with systematically varied sequences show that the contributions of steric effects predominantly influence the electronic structure and resulting trends in photophysical properties, while the interplay between size and hydrophobicity of individual residues becomes more significant for higher-order assemblies affecting bulk properties. This work demonstrates sequence-tunable molecular volume and polarity as synthetic handles to rationally modulate PDA material properties across length scales, providing insights into the programmability of biomimetic conjugated polymers with adaptive functionalities.
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Supramolecular materials, which rely on dynamic non-covalent interactions, present a promising approach to advance the capabilities of currently available biosensors. The weak interactions between supramolecular monomers allow for adaptivity and responsiveness of supramolecular or self-assembling systems to external stimuli. In many cases, these characteristics improve the performance of recognition units, reporters, or signal transducers of biosensors. The facile methods for preparing supramolecular materials also allow for straightforward ways to combine them with other functional materials and create multicomponent sensors. To date, biosensors with supramolecular components are capable of not only detecting target analytes based on known ligand affinity or specific host-guest interactions, but can also be used for more complex structural detection such as chiral sensing. In this Review, we discuss the advancements in the area of biosensors, with a particular highlight on the designs of supramolecular materials employed in analytical applications over the years. We will first describe how different types of supramolecular components are currently used as recognition or reporter units for biosensors. The working mechanisms of detection and signal transduction by supramolecular systems will be presented, as well as the important hierarchical characteristics from the monomers to assemblies that contribute to selectivity and sensitivity. We will then examine how supramolecular materials are currently integrated in different types of biosensing platforms. Emerging trends and perspectives will be outlined, specifically for exploring new design and platforms that may bring supramolecular sensors a step closer towards practical use for multiplexed or differential sensing, higher throughput operations, real-time monitoring, reporting of biological function, as well as for environmental studies.