Electron Hopping Across Hemin‐Doped Serum Albumin Mats on Centimeter‐Length Scales

Exploring long‐range electron transport across protein assemblies is a central interest in both the fundamental research of biological processes and the emerging field of bioelectronics. This work examines the use of serum‐albumin‐based freestanding mats as macroscopic electron mediators in bioelectronic devices. In particular, this study focuses on how doping the protein mat with hemin improves charge‐transport. It is demonstrated that doping can increase conductivity 40‐fold via electron hopping between adjacent hemin molecules, resulting in the highest measured conductance for a protein‐based material yet reported, and transport over centimeter length scales. The use of distance‐dependent AC impedance and DC current–voltage measurements allows the contribution from electron hopping between adjacent hemin molecules to be isolated. Because the hemin‐doped serum albumin mats have both biocompatibility and fabrication simplicity, they should be applicable to a range of bioelectronic devices of varying sizes, configurations, and applications.     

Light‐Driven Proton Transfer for Cyclic and Temporal Switching of Enzymatic Nanoreactors

Temporal activation of biological processes by visible light and subsequent return to an inactive state in the absence of light is an essential characteristic of photoreceptor cells. Inspired by these phenomena, light‐responsive materials are very attractive due to the high spatiotemporal control of light irradiation, with light being able to precisely orchestrate processes repeatedly over many cycles. Herein, it is reported that light‐driven proton transfer triggered by a merocyanine‐based photoacid can be used to modulate the permeability of pH‐responsive polymersomes through cyclic, temporally controlled protonation and deprotonation of the polymersome membrane. The membranes can undergo repeated light‐driven swelling–contraction cycles without losing functional effectiveness. When applied to enzyme loaded‐nanoreactors, this membrane responsiveness is used for the reversible control of enzymatic reactions. This combination of the merocyanine‐based photoacid and pH‐switchable nanoreactors results in rapidly responding and versatile supramolecular systems successfully used to switch enzymatic reactions ON and OFF on demand.     

First‐Layer Effect in Graphene‐Enhanced Raman Scattering

Graphene as a substrate for enhancing Raman scattering, called graphene‐enhanced Raman scattering (GERS), has been reported in previous work. Herein, it is found that the “first‐layer effect”, which is widely used to explain the chemical‐enhanced mechanism in surface‐enhanced Raman scattering (SERS), exists in the GERS system. The Langmuir–Blodgett (LB) technique is used to construct mono‐ and multilayer ordered aggregates of protoporphyrin IX (PPP). Raman spectra of PPP with different layer numbers of the LB film on graphene are collected. The Raman signal from the first monolayer LB film of PPP has a larger contribution to the Raman enhancement than that from subsequent monolayers. Meanwhile, the Raman enhancement is dependent on the molecular configuration in contact with graphene, in which the functional group of PPP in direct contact with graphene has a stronger enhancement than other groups. These results reveal that GERS is strongly dependent on the distance between graphene and the molecule, which is convincing evidence that the Raman enhancement effect based on graphene belongs to the chemical‐enhanced mechanism. This discovery provides a convenient system for the study of the chemical‐enhanced mechanism and will benefit further understanding of SERS.     

Highly Water‐Stable Lanthanide–Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence

Although proton conductors derived from metal–organic frameworks (MOFs) are highly anticipated for various applications including solid‐state electrolytes, H₂ sensors, and ammonia synthesis, they are facing serious challenges such as poor water stability, fastidious working conditions, and low proton conductivity. Herein, we report two lanthanide–oxalate MOFs that are highly water stable, with so far the highest room‐temperature proton conductivity (3.42 × 10^?3 S cm^?1) under 100% relative humidity (RH) among lanthanide‐based MOFs and, most importantly, luminescent. Moreover, the simultaneous response of both the proton conductivity and luminescence intensity to RH allows the linkage of proton conductivity with luminescence intensity. This way, the electric signal of proton conductivity variation versus RH will be readily translated to optical signal of luminescence intensity, which can be directly visualized by the naked eye. If proper lanthanide ions or even transition‐metal ions are used, the working wavelengths of luminescence emissions can be further extended from visible to near infrared light for even wider‐range applications.     

A Highly Reversible Long‐Life Li–CO2 Battery with a RuP2‐Based Catalytic Cathode

Rechargeable Li–CO₂ batteries have attracted worldwide attention due to the capability of CO₂ capture and superhigh energy density. However, they still suffer from poor cycling performance and huge overpotential. Thus, it is essential to explore highly efficient catalysts to improve the electrochemical performance of Li–CO₂ batteries. Here, phytic acid (PA)‐cross‐linked ruthenium complexes and melamine are used as precursors to design and synthesize RuP₂ nanoparticles highly dispersed on N, P dual‐doped carbon films (RuP₂‐NPCFs), and the obtained RuP₂‐NPCF is further applied as the catalytic cathode for Li–CO₂ batteries. RuP₂ nanoparticles that are uniformly deposited on the surface of NPCF show enhanced catalytic activity to decompose Li₂CO₃ at low charge overpotential. In addition, the NPCF its with porous structure in RuP₂‐NPCF provides superior electrical conductivity, high electrochemical stability, and enough ion/electron and space for the reversible reaction in Li–CO₂ batteries. Hence, the RuP₂‐NPCF cathode delivers a superior reversible discharge capacity of 11951 mAh g^?1, and achieves excellent cyclability for more than 200 cycles with low overpotentials (<1.3 V) at the fixed capacity of 1000 mAh g^?1. This work paves a new way to design more effective catalysts for Li–CO₂ batteries.     

Protein‐Bound Freestanding 2D Metal Film for Stealth Information Transmission

The welding and sintering of nanomaterials is usually achieved at high temperatures and high pressures. Here, it is found that merging of metal nanoparticles occurs under ambient conditions in an aqueous solution via protein bonding. It is discovered that the silver nanoparticles from the in situ reduction of silver ammonium ions by glucose undergo confined nucleation and growth and are bound by ultrathin amyloid‐like β‐sheet stacking of lysozyme. This merging of silver nanoparticles creates a freestanding large‐area (e.g., 400 cm²) 2D silver film at the air/water interface with a purity up to 98% and controls nanoscale thickness. This reaction system is general to other proteins and metals, and shows the great ability for controlled synthesis of highly reflective and highly conductive silver films with elongation nearly 10 times higher than that of pure metal without protein bonding. The ultrathin protein‐bonding layer functions as a key mediator to dynamically tune the silver conductance in response to external pressures and strains. The sensors exhibit ultrasensitive capability for stealth transmission of Morse code and for silent speech recording via the detection of tiny vibrations of the human throat. This approach will shed light on the development of protein bonding of a given material for bespoke functions.