Biological energy conversion is catalysed by proton-coupled electron transfer (PCET) reactions that form the chemical basis of respiratory and photosynthetic enzymes. Despite recent advances in structural, biophysical, and computational experiments, the mechanistic principles of these reactions still remain elusive. Based on common functional features observed in redox enzymes, we study here generic mechanistic models for water-mediated long-range PCET reactions. We show how a redox reaction within a buried protein environment creates an electric field that induces hydration changes between the proton acceptor and donor groups, and in turn, lowers the reaction barrier and increases the thermodynamic driving forces for the water-mediated PCET process. We predict linear free energy relationships, and discuss the proposed mechanism in context of PCET in cytochrome c oxidase.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6932871 | PMC |
| http://dx.doi.org/10.1039/c9cc01135h | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Evidence for a metal-bosonic insulator-superconductor transition in compressed sulfur.
Proc Natl Acad Sci U S A
January 2025
State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China.
The abrupt drop of resistance to zero at a critical temperature is a key signature of the current paradigm of the metal-superconductor transition. However, the emergence of an intermediate bosonic insulating state characterized by a resistance peak preceding the onset of the superconducting transition has challenged this traditional understanding. Notably, this phenomenon has been predominantly observed in disordered or chemically doped low-dimensional systems, raising intriguing questions about the generality of the effect and its underlying fundamental physics.
View Article and Find Full Text PDFDual-Anion-Rich Polymer Electrolytes for High-Voltage Solid-State Lithium Metal Batteries.
ACS Nano
January 2025
Department of Physics, JC STEM Lab of Energy and Materials Physics, City University of Hong Kong, Hong Kong 999077, P. R. China.
Solid polymer electrolytes (SPEs) are promising candidates for lithium metal batteries (LMBs) owing to their safety features and compatibility with lithium metal anodes. However, the inferior ionic conductivity and electrochemical stability of SPEs hinder their application in high-voltage solid-state LMBs (HVSSLMBs). Here, a strategy is proposed to develop a dual-anion-rich solvation structure by implementing ferroelectric barium titanate (BTO) nanoparticles (NPs) and dual lithium salts into poly(vinylidene fluoride) (PVDF)-based SPEs for HVSSLMBs.
View Article and Find Full Text PDFDetection of Extracochlear Electrodes Using Electrical Field Imaging (EFI).
Otol Neurotol
February 2025
Department of Otolaryngology-Head and Neck Surgery, Mayo Clinic, Rochester, Minnesota.
Objective: To analyze the use of electrical field imaging (EFI) in the detection of extracochlear electrodes in cochlear implants (CI).
Study Design: Retrospective cohort study.
Setting: Tertiary academic medical center.
Co-Atomic Interface Minimizing Charge Transfer Barrier in Polytypic Perovskites for CO Photoreduction.
Adv Sci (Weinh)
January 2025
School of Resources and Environment, University of Electronic Science and Technology of China, Chengdu, 611731, China.
Heterojunctions, known for their decent separation of photo-generated electrons and holes, are promising for photocatalytic CO reduction. However, a significant obstacle in traditional post-assembled heterojunctions is the high interfacial barrier for charge transfer caused by atomic lattice mismatch at multiphase interfaces. Here, as research prototypes, the study creates a lattice-matched co-atomic interface within CsPbBr-CsPbBr polytypic nanocrystals (113-125 PNs) through the proposed in situ hybrid strategy to elucidate the underlying charge transfer mechanism within this unique interface.
View Article and Find Full Text PDFPrecise Sizing and Collision Detection of Functional Nanoparticles by Deep Learning Empowered Plasmonic Microscopy.
Adv Sci (Weinh)
January 2025
Department of Chemistry, Center for BioAnalytical Chemistry, Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology, Tsinghua University, Beijing, 100084, China.
Single nanoparticle analysis is crucial for various applications in biology, materials, and energy. However, precisely profiling and monitoring weakly scattering nanoparticles remains challenging. Here, it is demonstrated that deep learning-empowered plasmonic microscopy (Deep-SM) enables precise sizing and collision detection of functional chemical and biological nanoparticles.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!