Quantitative analysis of the coupling between proton and electron transport in peptide/manganese oxide hybrid films.

Understanding how electrons and protons move in a coupled manner and affect one another is important to the design of proton-electron conductors and achieving biological transport in synthetic materials. In this study, a new methodology is proposed that allows for the quantification of the degree of coupling between electrons and protons in tyrosine-rich peptides and metal oxide hybrid films at room temperature under a voltage bias. This approach is developed according to the Onsager principle, which has been thoroughly established for the investigation of mixed ion-electron conductors with electron and oxide ion vacancies as carriers at high temperatures. Herein, a new device platform using electron-blocking electrodes provides a new strategy to investigate the coupling of protons and electrons in bulk materials beyond the molecular level investigation of coupled proton and electron transfer. Two Onsager transport parameters, αi* and σe', are obtained from the device, and the results of these transport parameters demonstrate that the coupled transport of electrons and protons inside the hybrid film plays an important role in the macroscopic-scale conduction. The results suggest that an average of one electron is dragged by one proton in the absence of a direct driving force for electron movement ∇ηe.

DNA translocation through a nanopore in an ultrathin self-assembled peptide membrane.

Here, we explore the possibility of using peptide-based materials as a membrane in solid-state nanopore devices in an effort to develop a sequence-specific, programmable biological membrane platform. We use a recently developed tyrosine-mediated self-assembly peptide sheet. At the air/water interface, the 5mer peptide YFCFY self-assembles into a uniform and robust two-dimensional (2D) structure, and the peptide sheet is easily transferred to a low-noise glass substrate. The thickness of the peptide membrane can be adjusted to approximately 5 nm (or even to 2 nm) by an etching process, and the diameters of the peptide nanopores can be precisely controlled using a focused electron beam with an attuned spot size. The ionic current noise of the peptide nanopore is comparable to those of typical silicon nitride nanopores or multilayer 2D materials. Using this membrane, we successfully observe translocation of 1000 bp double-stranded DNA with a sufficient signal-to-noise ratio of ∼30 and an elongated translocation speed of ∼1 bp µs-1. Our results suggest that the self-assembled peptide film can be used as a sensitive nanopore membrane and employed as a platform for applying biological functionalities to solid-state substrates.

Proton-enabled activation of peptide materials for biological bimodal memory.

The process of memory and learning in biological systems is multimodal, as several kinds of input signals cooperatively determine the weight of information transfer and storage. This study describes a peptide-based platform of materials and devices that can control the coupled conduction of protons and electrons and thus create distinct regions of synapse-like performance depending on the proton activity. We utilized tyrosine-rich peptide-based films and generalized our principles by demonstrating both memristor and synaptic devices. Interestingly, even memristive behavior can be controlled by both voltage and humidity inputs, learning and forgetting process in the device can be initiated and terminated by protons alone in peptide films. We believe that this work can help to understand the mechanism of biological memory and lay a foundation to realize a brain-like device based on ions and electrons.

Tyrosine-Rich Peptides as a Platform for Assembly and Material Synthesis.

The self-assembly of biomolecules can provide a new approach for the design of functional systems with a diverse range of hierarchical nanoarchitectures and atomically defined structures. In this regard, peptides, particularly short peptides, are attractive building blocks because of their ease of establishing structure-property relationships, their productive synthesis, and the possibility of their hybridization with other motifs. Several assembling peptides, such as ionic-complementary peptides, cyclic peptides, peptide amphiphiles, the Fmoc-peptide, and aromatic dipeptides, are widely studied. Recently, studies on material synthesis and the application of tyrosine-rich short peptide-based systems have demonstrated that tyrosine units serve as not only excellent assembly motifs but also multifunctional templates. Tyrosine has a phenolic functional group that contributes to π-π interactions for conformation control and efficient charge transport by proton-coupled electron-transfer reactions in natural systems. Here, the critical roles of the tyrosine motif with respect to its electrochemical, chemical, and structural properties are discussed and recent discoveries and advances made in tyrosine-rich short peptide systems from self-assembled structures to peptide/inorganic hybrid materials are highlighted. A brief account of the opportunities in design optimization and the applications of tyrosine peptide-based biomimetic materials is included.

Physically Transient Field-Effect Transistors Based on Black Phosphorus.

Black phosphorus (BP) has shown great potential as a semiconductor material beyond graphene and MoS2 because of its intrinsic band gap and high mobility. Moreover, the biocompatibility of the final biodegradation products of BP has led to extensive research on biomedical applications. Herein, physically transient field-effect transistors (FETs) based on black phosphorus have been demonstrated using peptide insulator as a gate dielectric layer. The fabricated devices show high hole mobility up to 468 cm2 V-1 s-1 and on-off current ratio over 103. The combined use of black phosphorus, peptide, and molybdenum provides rapid disappearance of the devices within 36 h. Dissolution kinetics and cytotoxicity of black phosphorus are assessed to clarify its availability to be applied in transient electronics. This work provides transient FETs with high degradability and high performance based on biocompatible black phosphorus.