Electron Transfer Reactions Research Articles

Role of cavity strong coupling on single electron transfer reaction rate at electrode-electrolyte interface.

The physicochemical properties of molecules can be modulated through polariton formation under strong electromagnetic confinement. Here, we discuss the possibility of exploiting this phenomenon to increase the electron transfer rate at an electrode-electrolyte interface. Electron transfer theory under strong electromagnetic confinement can be extended to the electrode-electrolyte interface, and single-electron transfer reactions can be simulated using Gerischer's theory. Although single electron transfer in free space is well described using Marcus theory, the vacuum electric field can facilitate an additional electron transfer pathway via virtual photon excitation under cavity strong coupling conditions. Therefore, this binary reaction pathway for single electron transfer can yield a quasi-two-particle electron transfer process. This quantum behavior can dominate when the mode volume is small and when there are a large number of molecules in the vacuum electric field. Exploitation of polaritons in single electron transfer reactions can lead to enhanced electrochemical energy conversion systems.

Basicity of MnIII-Hydroxo Complexes Controls the Thermodynamics of Proton-Coupled Electron Transfer Reactions.

Several manganese-dependent enzymes utilize MnIII-hydroxo units in concerted proton-electron transfer (CPET) reactions. We recently demonstrated that hydrogen bonding to the hydroxo ligand in the synthetic [MnIII(OH)(PaPy2N)]+ complex increased rates of CPET reactions compared to the [MnIII(OH)(PaPy2Q)]+ complex that lacks a hydrogen bond. In this work, we determine the effect of hydrogen bonding on the basicity of the hydroxo ligand and evaluate the corresponding effect on CPET reactions. Both [MnIII(OH)(PaPy2Q)]+ and [MnIII(OH)(PaPy2N)]+ react with strong acids to yield MnIII-aqua complexes [MnIII(OH2)(PaPy2Q)]2+ and [MnIII(OH2)(PaPy2N)]2+, for which we determined pKa values of 7.6 and 13.1, respectively. Reactions of the MnIII-aqua complexes with one-electron reductants yielded estimates of reduction potentials, which were combined with pKa values to give O-H bond dissociation free energies (BDFEs) of 77 and 85 kcal mol-1 for the MnII-aqua complexes [MnII(OH2)(PaPy2Q)]+ and [MnII(OH2)(PaPy2N)]+. Using these BDFEs, we performed an analysis of the thermodynamic driving force for phenol oxidation by these complexes and observed the unexpected result that slower rates are associated with more asynchronous CPET. In addition, reactions of acidic phenols with the MnIII-hydroxo complexes show rates that deviate from the thermodynamic trends, consistent with a change in mechanism from CPET to proton transfer.

Comparison of Au Nanoparticle/Poly(9-vinylcarbazole) Thin-Film Electrogeneration at 3 Distinct Liquid/Liquid Interfaces: Water/1,2-Dichloroethane, /α,α,α-Trifluorotoluene, Or/Ionic Liquid.

Metal nanoparticle (NP) incorporated conductive polymer films are attractive for their mechanical stability for biomedical applications and as heterogeneous electrocatalysis materials. Novel approaches to generate these materials with tunable properties are still being sought. Herein, the interface between two immiscible electrolyte solutions (ITIES) has been employed as a molecularly sharp and reproducible platform for simultaneous Au NP and poly(9-vinylcarbazole) generation. Three interfaces have been compared, including between water|1,2-dichloroethane (w|DCE), water|α,α,α-trifluorotoluene (w|TFT), and water|ionic liquid (w|IL). In this case the IL was P8888TB (tetraoctylphosphonium tetrakis(pentafluorophenyl)borate). 9-Vinylcarbazole (VC) can polymerize via two routes, either propagating through the vinyl substituent or the aryl rings. The former gives rise to a white semiconducting polymer with a wide bandgap, while the latter produces a green, conducting polymer. External potential control through voltammetric cycling was found to generate the film more rapidly favoring heterogeneous electron transfer with formation of the green poly(VC) variant at the ITIES. This was a free-standing film that could be easily removed from the interface. In the absence of external control, white polymer crystals formed within the oil phase spontaneously likely via AuCl4- w → o transfer followed by a homogeneous electron transfer reaction mechanism. Scanning electrochemical microscopy probe approach curve experiments were used to quantify the electroactivity of the film and are complemented by direct conductivity measurements.

Targeted Electrocatalysis for High‐Performance Lithium–Sulfur Batteries

The intricate sulfur redox chemistry involves multiple electron transfers and complicated phase changes. Catalysts have been previously explored to overcome the kinetic barrier in lithium–sulfur batteries (LSBs). This work contributes to closing the knowledge gap and examines electrocatalysis for enhancing LSB kinetics. With a strong chemical affinity for polysulfides, the electrocatalyst enables efficient adsorption and accelerated electron transfer reactions. Resulting cells with catalyzed cathodes exhibit improved rate capability and excellent stability over 500 cycles with 91.9% capacity retention at C/3. In addition, cells were shown to perform at high rates up to 2C and at high sulfur loadings up to 6 mg cm−2. Various electrochemical, spectroscopic, and microscopic analyses provide insights into the mechanism for retaining high activity, coulombic efficiency, and capacity. This work delves into crucial processes identifying pivotal reaction steps during the cycling process at commercially relevant areal capacities and rates.

Optical Quantum Control of the Electron Transfer Reactions in Protein Flavodoxin.

The optical quantum control has been successfully applied in modulating biological processes such as energy transfer and bond isomerization. Among the reactions in realizing biological functions, the electron transfer (ET) process is fundamental; hence, the quantum control over such an ET reaction is of far-reaching significance. Here, we realized optical quantum control over ultrafast ET processes in a protein, flavodoxin, by applying various chirped excitation pulses. We observed the wavepacket dynamics within a dephasing time of less than 1 ps. Within this time window, we found that the ultrafast photoinduced ET reaction can be controlled by different chirped excitations with a rate change by a factor of about 2. Furthermore, the control effect is propagated into the subsequent ultrafast back ET reaction, showing a variation of the BET dynamics with different excitation chirps. The underlying mechanism is the initial wavepacket dynamics; the differently prepared wavepackets with chirped excitation evolve along various pathways, resulting in the changes of ET rates. The successful demonstration of optical quantum control of ultrafast biological ET is significant and opens a new avenue to explore the quantum control of real biological ET reactions.

Cobalt-modified digestate-derived biochar enhances kitchen waste anaerobic dry digestion: Performance, microbial mechanisms, and metabolic pathways

To achieve simultaneous in-situ high-value utilization of digestate and efficient resource recovery of kitchen waste (KW). In this work, Co-modified digestate-derived biochar (DDB-Co) was prepared for the first time, the effects of DDB-Co on KW mesophilic dry anaerobic digestion were investigated, and the underlying mechanisms were elucidated. The results showed that the specific surface area of DDB-Co increased to 98.7 m2/g, which was 37.4 % higher than that of the unmodified group (DDB). DDB-Co exhibited a dose-dependent effect on biogas production from the KW dry digestion, with the optimal dose of 4.0 g/L (calculated on a solid content) DDB-Co yielding 205.3 mL/(g·VS) of biogas, representing an 80.9 % increase compared to the CK group. However, higher doses, such as 8.0 g/L DDB-Co, reduced the cumulative biogas production. Mechanistic analysis indicated that 4.0 g/L DDB-Co facilitated the dissolution of particulate organic matter and accelerates the conversion process of volatile fatty acids (VFA) in KW, thereby preventing excessive acidification. Microbial community structure analysis revealed that DDB-Co reduced microbial richness and diversity but selectively enriched microorganisms such as Lactobacillus and Methanothrix, accelerating the direct interspecific electron transfer (DIET) reaction rate and increasing biogas production. Metagenomic analysis demonstrated that DDB-Co primarily upregulated the relative abundances of key enzymes in the acetate decarboxylation methanogenesis pathway, such as acetate kinase (ackA), phosphate acetyltransferase (pta), and acetyl-CoA synthetase (acs), enhancing biogas yield and maintaining system stability. The findings of this work expand the high-value utilization pathways for digestate and provide an alternative solution for the efficient resource recovery of KW.

Insights into a photo-driven laccase coupling system for enhanced photocatalytic oxidation and biodegradation

Effective depolymerization of lignin into environmentally friendly aromatic chemicals under mild conditions is gaining interest. Fungal laccase is capable of catalyzing a wide range of reactions, but its low redox potential and preference for acidic pH limit its potential applications. Herein, we developed a laccase-methylene blue (LAC-MB) coupling system, combining the selectivity of enzyme catalysis with the high reactivity of photocatalysis, for the efficient degradation of lignin model compounds. Theoretical calculations indicate that the electron donor’s distance to the LAC’s active site T1 Cu is shortened from 29.7 to 7.3 Å in the LAC-MB. In this system, MB, possessing strong interaction with T1 Cu, acts as a light absorber, enabling the rapid transfer of photogenerated electrons to T1 Cu. This significantly enhances the degradation rate of guaiacol (GUA) from 28.8 % to 91.46 %. The LAC-MB can oxidize both phenolic and non-phenolic lignin model compounds under red-LED irradiation with wide pH ranging from 3.0 to 7.0 and high-efficiency. By tuning the primary coordination sphere and the access tunnel of T1 Cu, we further revealed that enhanced binding affinity and active site accessibility for the LAC-MB complex attributed to the photocatalysis’s high reactivity. Based on this, LAC variants with enhanced binding capabilities were constructed and the resulting mutant LAC-MB are characterized by higher oxygen consumption and ROS generation activated by red-LED, specifically a higher quantum yield of 1O2, demonstrating increased electron transfer and light-driven reactivity. This photo-enzyme coupling system presents a new pathway for the high-efficiency processing of lignocellulosic biomass and offers insights for designing future artificial photosynthetic systems.

Electrochemically Determined and Structurally Justified Thermochemistry of H atom Transfer on Ti-Oxo Nodes of the Colloidal Metal-Organic Framework Ti-MIL-125.

Titanium dioxide (TiO2) has long been employed as a (photo)electrode for reactions relevant to energy storage and renewable energy synthesis. Proton-coupled electron transfer (PCET) reactions with equimolar amounts of protons and electrons at the TiO2 surface or within the bulk structure lie at the center of these reactions. Because a proton and an electron are thermochemically equivalent to an H atom, these reactions are essentially H atom transfer reactions. Thermodynamics of H atom transfer has a complex dependence on the synthetic protocol and chemical history of the electrode, the reaction medium, and many others; together, these complications preclude the understanding of the H atom transfer thermochemistry with atomic-level structural knowledge. Herein, we report our success in employing open-circuit potential (EOCP) measurements to quantitatively determine the H atom transfer thermochemistry at structurally well-defined Ti-oxo clusters within a colloidally stabilized metal-organic framework (MOF), Ti-MIL-125. The free energy to transfer H atom, Ti3+O-H bond dissociation free energy (BDFE), was measured to be 68(2) kcal mol-1. To the best of our understanding, this is the first report on using EOCP measurements to quantify thermochemistry on any MOFs. The proton topology, the structural change upon the redox reaction, and BDFE values were further quantitatively corroborated using computational simulations. Furthermore, comparisons of the EOCP-derived BDFEs of Ti-MIL-125 to similar parameters in the literature suggest that EOCP should be the preferred method for quantitatively accurate BDFE calculations. The reported success in employing EOCP for nanosized Ti-MIL-125 should lay the ground for thermochemical measurements of other colloidal systems, which are otherwise challenging. Implications of these measurements on Ti-MIL-125 as an H atom acceptor in chemical reactions and comparisons with other MOFs/metal oxides are discussed.

In Situ FT-IR Spectroelectrochemistry Reveals Mechanistic Insights into Nitric Oxide Release from Ruthenium(II) Nitrosyl Complexes.

Ruthenium(II) tetraamine nitrosyl complexes with N-heterocyclic ligands are known for their potential as nitric oxide (NO•) donors, capable of releasing NO• through either direct photodissociation or one-electron reduction of the Ru(II)NO+ center. This study delivers a novel insight into the one-electron reduction mechanism for the model complex trans-[RuII(NO)(NH3)4(py)]3+ (RuNOpy, py = pyridine) in phosphate buffer solution (pH 7.4). In situ FT-IR spectroelectrochemistry reveals that the pyridine ligand is readily released upon one-electron reduction of the nitrosyl complex, a finding supported by nuclear magnetic resonance spectroscopy (1H NMR) and electrochemistry coupled to mass spectrometry (EC-MS), which detect free pyridine in solution. However, direct evidence of NO• release from RuNOpy as the primary step following reduction was not observed. Interestingly, FT-IR results indicate that the isomers of the nitrosyl complex, cis-[Ru(NO)(NH3)4(OH)]+ and trans-[Ru(NO)(NH3)4(OH)]+, are formed following reduction and pyridine labilization, initiating an outer-sphere electron transfer process that triggers a chain electron transfer reaction. Finally, nitric oxide is liberated as an end product, arising from the reduction of the hydroxyl isomer complexes cis-[Ru(NO)(NH3)4(OH)]2+ and trans-[Ru(NO)(NH3)4(OH)]2+. This study provides new insights into the reduction mechanism and transformation pathways of ruthenium nitrosyl complexes, contributing to our understanding of their potential as NO• donors.

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal-Ligand Cooperativity.

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [CoIIICp(PPh2NBn2)(CH3CN)]2+ to [HCoIIICp(PPh2NBn2)]+. This complex catalytically converts CO2 to formate under CO2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the PPh2NBn2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the PPh2NBn2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pKa values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. This work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

Heteromultimetallic Platform for Enhanced C-H Bond Activation: Aluminum-Incorporated Dicopper Complex Mimicking Cu-ZSM-5 Structure and Oxidative Reactivity.

Bimetallic complexes have sparked interest across various chemical disciplines, driving advancements in research. Recent advancements in this field have shed light on complex reactions in metalloenzymes and unveiled new chemical transformations. Two primary types of bimetallic platforms have emerged: (1) systems where both metals actively participate in reactivity, and (2) systems where one metal mediates the reaction while the other regulates reactivity. This study introduces a novel multinucleating ligand platform capable of integrating both types of bimetallic systems. To demonstrate the significance of this platform, we synthesized a unique dicopper complex incorporating aluminum in its coordination environment. This complex serves as the first structural model for the active site in copper-based zeolites, highlighting the role of aluminum in hydrogen atom abstraction reactivity. Comparative studies of oxidative C-H bond activation revealed that the inclusion of aluminum significantly alters the thermodynamic driving force (by -11 kcal mol-1) for bond activation and modifies the proton-coupled electron-transfer reaction mechanism, resulting in a 14-fold rate increase. Both computational and experimental data support the high modularity of this multinucleating ligand platform, offering a new approach to fine-tune the reactivity of bimetallic complexes.

Attenuating Nucleophilicity of Titanocene Hydrides Beyond Steric Effects en Route to Fatty Alcohols.

Here, we introduce a new class of titanocene catalysts for epoxide hydrosilylation that frustrates their hydridicity and thereby emphasizes their electron transfer reactivity. This unique attenuation of hydridicity is accomplished by introducing Lewis acidic silicon centers to the cyclopentadienyl ligands for an intramolecular coordination of the titanium-bound hydride. The superiority of our rationally designed catalysts over classic titanocenes with alkyl-substituted cyclopentadienyl ligands is demonstrated in the dramatically improved regioselectivity of the hydrosilylation of monosubstituted epoxides to primary alcohols.

Geranylgeranylated-chlorophyll-protein complexes in lhl3 mutant of the green alga Chlamydomonas reinhardtii.

Chlorophylls a and b (Chl a and b) are involved in light harvesting, photochemical reactions, and electron transfer reactions in plants and green algae. The core complexes of the photosystems (PSI and PSII) associate with Chl a, while the peripheral antenna complexes (LHCI and LHCII) bind Chls a and b. One of the final steps of Chl biosynthesis is the conversion of geranylgeranylated Chls (ChlsGG) to phytylated Chls by geranylgeranyl reductase (GGR). Here, we isolated and characterized a pale green mutant of the green alga Chlamydomonas reinhardtii that was very photosensitive and was unable to grow photoautotrophically. This mutant has a 16-bp deletion in the LHL3 gene, which resulted in the loss of LHL3 and GGR and accumulated only ChlsGG. The lhl3 mutant cells grown in the dark accumulated PSII and PSI proteins at 25-50% of WT levels, lacked PSII activity, and retained a decreased PSI activity. The PSII and PSI proteins were depleted to trace amounts in the mutant cells grown in light. In contrast, the accumulation of LHCI and LHCII was unaffected except for LHCA3. Our results suggest that the replacement of Chls with ChlsGG strongly affects the structural and functional integrity of PSII and PSI complexes but their associating LHC complexes to a lesser extent. Affinity purification of HA-tagged LHL3 confirmed the formation of a stable LHL3-GGR complex, which is vital for GGR stability. The LHL3-GGR complex contained a small amount of PSI complex assembly factors, suggesting a putative coupling between Chl synthesis and PSI complex assembly.

Dehydrogenative Coupling Reactions with Guanidino-Functionalized Aromatics.

Dehydrogenative coupling (DC) reactions are of importance for the construction of new carbon-element bonds in synthetic organic chemistry. In this work, we report on the synthesis and characterization of several redox-active guanidino-functionalized aromatic molecules (GFAs) for use in DC (C-C and C-O) reactions. In a systematic approach, we first characterize the new DC reagents in all relevant redox and protonation states, and compare their performance in competitive test proton-coupled electron transfer (PCET) reactions. Then, their use in four different DC reactions with different mechanisms is evaluated.

In situ construction of W-doped Co-P electrocatalyst by electrodeposition for boosting alkaline water/seawater hydrogen evolution reaction

The development of an efficient yet cost-effective non-precious electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water and seawater systems remains a formidable obstacle to the large-scale production of hydrogen energy, stemming from the sluggish kinetics of electron transfer reactions during the HER process. In this article, an amorphous Co-P-W electrocatalyst on nickel foam is prepared using a brief cyclic voltammetry (CV) electrodeposition method. The optimized Co-P-W electrocatalyst exhibits excellent electrocatalytic performance for HER, which only requires overpotentials of 59 and 143 mV to achieve a current density of 10 mA cm−2 in alkaline water (1.0 M KOH) and alkaline seawater (1.0 M KOH + natural seawater), respectively, and remarkable stability and durability. The improved HER performance of the Co-P-W electrocatalyst is attributed to the introduction of W, which modulates the electronic structure of Co and P, optimizes the adsorption/dissociation of H2O, and reduces the charge transfer resistance of the Co-P electrocatalyst, thus improving the kinetics of the HER. Furthermore, the W-doping significantly enhances the hydrophilicity of the Co-P electrocatalyst, which favors rapid and thorough penetration of electrolytes into the electrocatalyst, facilitating the formation of a highly accessible reaction interface, ultimately resulting in excellent HER activity. Our findings demonstrate the feasibility of designing an efficient, durable, and scalable electrocatalyst to significantly boost HER efficiency for practical water electrolysis.

High‐performance vanadium oxide‐based aqueous zinc batteries: Organic molecule modification, challenges, and future prospects

AbstractAqueous Zn‐vanadium batteries have been attracting significant interest due to the high theoretical capacity, diverse crystalline structures, and cost‐effectiveness of vanadium oxide cathodes. Despite these advantages, challenges such as low redox potential, sluggish reaction kinetics, and vanadium dissolution lead to inferior energy density and unsatisfactory lifespan of vanadium oxide cathodes. Addressing these issues, given the abundant redox groups and flexible structures in organic compounds, this study comprehensively reviews the latest developments of organic‐modified vanadium‐based oxide strategies, especially organic interfacial modification, and pre‐intercalation. The review presents detailed analyses of the energy storage mechanism and multiple electron transfer reactions that contribute to enhanced battery performance, including boosted redox kinetics, higher energy density, and broadened lifespan. Furthermore, the review emphasizes the necessity of in situ characterization and theoretical calculation techniques for the further investigation of appropriate organic “guest” materials and matched redox couples in the organic‐vanadium oxide hybrids with muti‐energy storage mechanisms. The review also highlights strategies for Zn anode protection and electrolyte solvation regulation, which are critical for developing advanced Zn‐vanadium battery systems suitable for large‐scale energy storage applications.

Synergetic effect of pyrrhotite and zero-valent iron on Hg(Ⅱ) removal in constructed wetland: Mechanisms of electron transfer and microbial reaction

Effective removal of mercury (Hg) from wastewater is significant due to its high toxicity, especially methylmercury (MeHg). Reducing of Hg(II) to Hg(0) in constructed wetlands (CWs) using iron-based materials is an effective strategy for preventing the formation of MeHg. However, the surface passivation of zero-valent iron (ZVI) limits its application. Herein, synergetic ZVI and pyrrhotite were utilized to enhance Hg removal in CWs. Results indicated that the removal of total Hg, dissolved Hg, and particulate Hg in CWs with ZVI and pyrrhotite were improved by 21.68 ± 0.76 %, 13.02 ± 0.88 %, and 22.27 ± 0.76 % compared to that with single ZVI or pyrrhotite. Pyrrhotite increased the surface corrosion of ZVI, thereby facilitating the process of iron reduction. The redox of iron promoted the generation of EPS, which could provide electrons for Hg(II) reduction. The sulfur also participates in electron transfer by driving the methylation of Hg and provides sulfides to form FeS-Hg complexes and HgS precipitation. The abundance of key enzymes that involved in iron reduction and Hg transformation was enhanced with the addition of ZVI and pyrrhotite. The synergetic of pyrrhotite and ZVI enhances the removal of Hg in CW, offering a promising technology for high-efficiency treatment of Hg.

Finding the E-channel proton loading sites by calculating the ensemble of protonation microstates

The aerobic electron transfer chain builds a proton gradient by proton coupled electron transfer reactions through a series of proteins. Complex I is the first enzyme in the sequence. Here transfer of two electrons from NADH to quinone yields four protons pumped from the membrane N- (negative, higher pH) side to the P- (positive, lower) side. Protons move through three linear antiporter paths, with a few amino acids and waters providing the route; and through the E-channel, a complex of competing paths, with clusters of interconnected protonatable residues.Proton loading sites (PLS) transiently bind protons as they are transported from N- to P-compartments. PLS can be individual residues or extended clusters of residues. The program MCCE uses Monte Carlos sampling to analyze the E-channel proton binding in equilibrium with individual Molecular Dynamics snapshots from trajectories of Thermus thermuphillus Complex I in the apo, quinone and quinol bound states. At pH 7, the five E-channel subunits (Nqo4, Nqo7, Nqo8, Nqo10, and Nqo11) take >25,000 protonation microstates, each with different residues protonated. The microstate explosion is tamed by analyzing interconnected clusters of residues along the proton transfer paths. A proton is bound and released from a cluster of five coupled residues on the protein N-side and to six coupled residues in the protein center. Loaded microstates bind protons to sites closer to the P-side in the forward pumping direction. MCCE microstate analysis identifies strongly coupled proton binding amongst individual residues in the two PLS clusters.

Protein Medium Facilitates Electron Transfer in Photosynthetic Heliobacterial Reaction Center.

This computational study addresses the question of how large membrane-bound proteins of electron transport chains facilitate fast vector-based charge transport. We study electron transfer reactions following ultrafast initial charge separation induced by absorption of light by P800 primary pair and leading to the electron localization at the A0 cofactor. Two subsequent, much slower reactions, electron transfer to the iron-sulfur cluster Fx and reduction of the menaquinone (MQ) cofactor, are studied by combining molecular dynamics simulations, electronic structure calculations, and theoretical modeling. The low value of the electronic coupling between A0 and Fx brings this reaction to the microsecond time scale even at the zero activation barrier. In contrast, A0-MQ electron transfer occurs on a subnanosecond time scale and might become the preferred route for charge transport. We elucidate mechanistic properties of the protein medium allowing fast, vectorial charge transfer. The electric field is high and inhomogeneous inside the protein and is coupled to high polarizabilities of cofactors to significantly lower the reaction barrier. The A0-MQ separation puts this reaction at the edge between the plateau characterizing the reaction dynamical control and exponential falloff due to electronic tunneling. A strong separation in relaxation times of the medium dynamics for the forward and backward reactions promotes vectorial charge transfer.

Molecular switching by proton-coupled electron transport drives giant negative differential resistance

To develop new types of dynamic molecular devices with atomic-scale control over electronic function, new types of molecular switches are needed with time-dependent switching probabilities. We report such a molecular switch based on proton-coupled electron transfer (PCET) reaction with giant hysteric negative differential resistance (NDR) with peak-to-valley ratios of 120 ± 6.6 and memory on/off ratios of (2.4 ± 0.6) × 103. The switching dynamics probabilities are modulated by bias voltage sweep rate and can also be controlled by pH and relative humidity, confirmed by kinetic isotope effect measurements. The demonstrated dynamical and environment-specific modulation of giant NDR and memory effects provide new opportunities for bioelectronics and artificial neural networks.