Single Electron 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.

Modelling the Repair of Carbon-Centered Protein Radicals by Phenolic Antioxidants

Oxidative stress is a biological process that has been linked to many diseases, hence understanding how to prevent and repair it is essential to medicine. The thermodynamics and kinetics of the repair reactions of radically damaged leucine (a lateral chain in a simplified protein environment) by twenty phenolic antioxidants are studied at the M06-2X(SMD)/6-31++G(d,p) level of theory in water and pentyl ethanoate. The two repair mechanisms modelled are formal-hydrogen atom transfer (f-HAT) and single electron transfer (SET). Although all f-HAT reactions are thermodynamically favourable, only one of the phenols produced rate constants in the diffusion limit, exhibiting biological relevance. SET is not suspected to be an important repair pathway for the phenols studied. We show that the Bell–Evans–Polanyi principle, which relates thermodynamics and kinetics properties for a reaction, breaks down when comparing between the solvents, protein repair sites, and the phenolic antioxidants. While thermodynamic data can be used as valuable screening tools, the kinetic calculation of rate constants in solution is crucial for enhancing the biological relevance of theoretical studies.

The electronic properties of a single electron in the GaAs/Ga1−xAlxAs oblate spheroidal quantum dot under the finite confinement potential

Quantum Dots, due to their fully quantized electronic states, have contributed to considerable progress in modern science and technology. Here we calculate the wave functions and energy spectrum of an electron confined in an oblate spheroidal quantum dot under the finite barrier potential condition, allowing the tailoring of the various energy states for specific applications. By calculating the electron wave functions outside the dot, we found that an infinite barrier is not a valid approximation for analyzing the optical properties of the structure. The effect of various geometrical and electrical characteristics of the structure, including the eccentricity, effective volume, and the height of barrier potential, is investigated. Additionally, the findings are compared with those found with prolate spheroidal quantum dot. The findings are further validated by comparing them to the exact electron energy level in a spherical quantum under the infinite barrier approximation.

Visible‐Light‐Driven Glycosylation Mediated by Trifluoromethyl Thianthrenium Triflate with Thioglycoside Donors

AbstractAn efficient photoredox‐catalyzed glycosylation using a p‐tolyl thioglycoside donor in the presence of trifluoromethyl thianthrenium triflate (TT‐CF3+TfO−) has been investigated. This approach involves generating a trifluoromethyl radical via single electron transfer between TT‐CF3+TfO− and the photocatalyst Rose Bengal, thereby activating thioglycosides and facilitating glycosylation. This method operates under mild reaction conditions and tolerates a variety of functional groups.

α-Trifluoromethylated Quinolines as Safe and Storable PET-Donor for Radical Polymerizations.

In the quest for powerful, safe, and storable photoinduced-electron transfer (PET) donors, the attention is turned to the α-trihalomethylated amine moiety that is not studied in the context of PET-reductants. The thermal and photophysical properties of α-trifluoromethylated quinolines are thus studied and their reducing abilities evaluated as initiators of polymerization reactions. Polymers of high molecular weights are obtained through a radical polymerization process and the PET-donor can be stored within the monomer for several months without losing its efficiency. Mechanistic investigations, combining spectroscopic analysis and theoretical calculations, confirm the mode of activation of these electron donors and the generation of radical intermediates through single electron transfer.

Harmonizing Visible‐Light in Green Synthesis: Unrevealing the Brilliance of Metal‐Free Cross‐Coupling of Unsaturated Hydrocarbons for C−C Bonds Formation

AbstractVisible‐light induced, photoredox catalysis has opened a wide range in the transformation of organic compounds in recent times. In synthetic organic chemistry HAT (hydrogen atom transfer) and SET (single electron transfer) mechanisms are a very noteworthy routes that has opened a window in favor of C−C single bond formations. Usually, a major role of unsaturated hydrocarbons is to participate in carbon‐carbon bond formation as they carry reactive π‐bond. Under visible‐light, metal‐free cross‐coupling reactions are particularly favorable because of their atom economy, increased efficiency, and environmentally friendly procedures that result in the construction of C−C bonds. The review emphasizes the latest advancements of visible‐light mediated, cross‐coupling reactions of unsaturated hydrocarbons in metal‐free conditions for constructing carbon‐carbon single bonds.

Unique structural attributes of the PSI-NDH supercomplex in Physcomitrium patens.

Cyclic electron transport around photosystem I (PSI) is essential for the protection of the photosynthetic apparatus in plants under diverse light conditions. This process is primarily mediated by Proton Gradient Regulation 5 protein/Proton Gradient Regulation 5-like photosynthetic phenotype 1 protein (PGR5/PGRL1) and NADH dehydrogenase-like complex (NDH). In angiosperms, NDH interacts with two PSI complexes through distinct monomeric antennae, LHCA5 and LHCA6, which is crucial for its higher stability under variable light conditions. This interaction represents an advanced evolutionary stage and offers limited insight into the origin of the PSI-NDH supercomplex in evolutionarily older organisms. In contrast, the moss Physcomitrium patens (Pp), which retains the lhca5 gene but lacks the lhca6, offers a glimpse into an earlier evolutionary stage of the PSI-NDH supercomplex. Here we present structural evidence of the Pp PSI-NDH supercomplex formation by single particle electron microscopy, demonstrating the unique ability of Pp to bind a single PSI in two different configurations. One configuration closely resembles the angiosperm model, whereas the other exhibits a novel PSI orientation, rotated clockwise. This structural flexibility in Pp is presumably enabled by the variable incorporation of LHCA5 within PSI and is indicative of an early evolutionary adaptation that allowed for greater diversity at the PSI-NDH interface. Our findings suggest that this variability was reduced as the structural complexity of the NDH complex increased in vascular plants, primarily angiosperms. This study not only clarifies the evolutionary development of PSI-NDH supercomplexes but also highlights the dynamic nature of the adaptive mechanisms of plant photosynthesis.

Theoretical Study of the Magnetic Mechanism of a Pca21 C4N3 Monolayer and the Regulation of Its Magnetism by Gas Adsorption

For metal-free low-dimensional ferromagnetic materials, a hopeful candidate for next-generation spintronic devices, investigating their magnetic mechanisms and exploring effective ways to regulate their magnetic properties are crucial for advancing their applications. Our work systematically investigated the origin of magnetism of a graphitic carbon nitride (Pca21 C4N3) monolayer based on the analysis on the partial electronic density of states. The magnetic moment of the Pca21 C4N3 originates from the spin-split of the 2pz orbit from special carbon (C) atoms and 2p orbit from N atoms around the Fermi energy, which was caused by the lone pair electrons in nitrogen (N) atoms. Notably, the magnetic moment of the Pca21 C4N3 monolayer could be effectively adjusted by adsorbing nitric oxide (NO) or oxygen (O2) gas molecules. The single magnetic electron from the adsorbed NO pairs with the unpaired electron in the N atom from the substrate, forming a Nsub-Nad bond, which reduces the system’s magnetic moment from 4.00 μB to 2.99 μB. Moreover, the NO adsorption decreases the both spin-down and spin-up bandgaps, causing an increase in photoelectrical response efficiency. As for the case of O2 physisorption, it greatly enhances the magnetic moment of the Pca21 C4N3 monolayer from 4.00 μB to 6.00 μB through ferromagnetic coupling. This method of gas adsorption for tuning magnetic moments is reversible, simple, and cost-effective. Our findings reveal the magnetic mechanism of Pca21 C4N3 and its tunable magnetic performance realized by chemisorbing or physisorbing magnetic gas molecules, providing crucial theoretical foundations for the development and utilization of low-dimensional magnetic materials.

LabEmbryoCam: An opensource phenotyping system for developing aquatic animals

Phenomics is the acquisition of high-dimensional data on an individual-wide scale and is proving transformational in areas of biological research related to human health including medicine and the crop sciences. However, more broadly, a lack of accessible transferrable technologies and research approaches is significantly hindering the uptake of phenomics, in contrast to molecular-omics for which transferrable technologies have been a significant enabler. Aquatic embryos are natural models for phenomics, due to their small size, taxonomic diversity, ecological relevance, and high levels of temporal, spatial and functional change. Here, we present LabEmbryoCam, an autonomous phenotyping platform for timelapse imaging of developing aquatic embryos cultured in a multiwell plate format, and while optimised for embryos, the instrument is extremely versatile. The LabEmbryoCam capitalises on 3D printing, single board computers, consumer electronics and stepper motor enabled motion. These provide autonomous X, Y and Z motion, a web application streamlined for rapid setup of experiments, user email notifications and a humidification chamber to reduce evaporation over prolonged acquisitions. Downstream analyses are provided, enabling automated embryo segmentation, heartbeat detection, motion tracking, and energy proxy trait (EPT) measurement. LabEmbryoCam is a scalable, and flexible laboratory instrument, that leverages embryonic and early life stage organisms to tackle key global challenges including biological sensitivity assessment, toxicological screening, but also to support broader engagement with the earliest stages of life.

High-Valent Iron–Oxo species in heterogeneous Catalysis: Formation, Mechanism, and reactivity for the degradation of various emerging organic contaminants

High-valent iron–oxo species (FeⅣ/Ⅴ=O), generated via peroxide activation with Fe-based catalysts, have shown potential in the selective and efficient degradation of organic contaminants. However, a comprehensive understanding of the oxidative degradation mechanism induced by FeⅣ/Ⅴ=O is still pending. In this research, to unravel this oxidation mechanism, an Fe-single atom catalyst (FeN4-C) was synthesized, and FeⅤ=O was formed as the predominant reactive species upon peroxymonosulfate (PMS) activation. The FeN4-C/PMS system was experimentally studied on its catalytic oxidation behavior for the degradation of 34 typical emerging organic contaminants (EOCs) in water, exhibiting a significant variation in the pseudo first-order kinetic rate constants (kobs) among the EOCs. A quantitative structure–activity relationship (QSAR) model was established based on the molecular structure feature and measured kobs of the EOCs. The model infers that EOCs with higher electron donating ability (EHOMO) are more susceptible towards FeN4-C/PMS oxidation, implying an electrophilic reaction following the single electron transfer (SET) mechanism. Further exploration of the degradation pathways for seven representative EOCs revealed that the oxidation occurs through the abstraction of either a hydrogen atom or a nonbonded (or π) electron by FeⅤ=O, enabling processes such as C-, N-, and S-oxidation, along with N- and O-dealkylation and deamination, to effectively degrade EOCs. These research findings provide a robust theoretical framework for understanding the reaction mechanisms and predicting the degradability and removal of various EOCs by FeⅣ/Ⅴ=O for water purification.

The degradation of methyl orange by OH radicals in aqueous environments: A DFT study on the mechanism, kinetics, temperature and pH effects

Methyl orange (MO) is extensively used in the food, textile, leather, and paper industries. As with many industrial chemicals, while primary environmental effects are documented, the secondary effects from its natural degradation have not been fully established. This study employs quantum chemical calculations to investigate the reaction of MO with HO• radicals that is a typical breakdown pathway in aqueous environments. It was found that the HO• + MO reaction in water can occur via either hydrogen transfer, single electron transfer, or radical adduct formation mechanisms, resulting in a variety of metastable intermediates and products. The calculated total rate constant (ktotal = 2.43×1010 M−1 s−1 at 298 K, pH = 9.2) is in good agreement with the experimental rate constant (kExp = (2.0 ± 0.3) ×1010 M−1 s−1at 298 K, pH = 9.2), thus confirming the accuracy of the calculation method. MO can degrade in natural water within the broad time range of 3.28 hrs to 56.6 years. The breakdown of methyl orange by HO• radicals is more effective at high temperatures and basic pH levels.

A Direct Visible‐Light Mediated Coupling Of Azaarenes with Diversely Functionalized Alkyl Carbons via Organophotocatalytic Sp3C−H Bond Activation

AbstractSubstituted azaarenes are one of the most ubiquitous moieties in natural products and drug molecules. An efficient organophotocatalytic method for direct coupling of diverse cyclic and acyclic alkyl carbons of alcohols, ethers, alkyl halides and alkanes with different azaaryl systems has been developed. It uses low loading of easily synthesizable efficient acridinium based photocatalyst and blue LED to generate highly reactive radicals on saturated hydrocarbons through sequential single electron transfer (SET) and hydrogen atom transfer (HAT) process. These in situ generated nucleophilic carbon radicals then undergo instantaneous regio‐selective coupling with azaarenes through Minisci type coupling to generate an array of important pharmacophores through sp2C−sp3C bond formation. With inexpensive organophotocatalysts, higher yield and wide substrate scope, this method provides a greener, efficient and versatile alternative to the previously reported syntheses.

Reactions of Diphenylamine with OH Radicals in the Environment: Theoretical Insights into the Mechanism, Kinetics, Temperature, and pH Effects.

Diphenylamine (DPL) has been widely utilized in industrial chemicals, but its degradation by HO• radicals in the environment has not been fully studied yet. The present study uses quantum chemical calculations to evaluate the reaction of DPL with HO• radicals in atmospheric and aqueous environments. The results showed that, in the atmosphere, the diphenylamine reacted with the HO• radical rapidly, with an overall rate constant of 9.24 × 1011 to 1.34 × 1011 M-1 s-1 and a lifetime of 0.17 to 1.55 h at 253-323 K. The calculated overall rate constant in water (koverall = 1.95 × 1010 M-1 s-1, pH = 3-14) is in excellent agreement with the experimental value (koverall = 1.00 × 1010-1.36 × 1010 M-1 s-1). The HO• + DPL reaction in water could occur following the hydrogen transfer (15.4%), single electron transfer (41.6%), and radical adduct formation (41.7%) mechanisms, clarifying that addition products were not exclusive products. Nevertheless, variations in temperature and pH within aqueous environments had an impact on the mechanisms, kinetics, and degradation products of the reaction of DPL with HO• radicals.

Photoredox-Catalyzed Markovnikov Hydroamination of Alkenes with Azoles.

A visible-light induced intermolecular hydroamination of alkenes with azoles is reported, delivering pharmaceutically valuable N-benzyl azoles in high yields with excellent Markovnikov selectivity. Mechanistic studies suggest that the process is initiated by the energy transfer of the excited photocatalyst with alkenes, followed by the single electron reduction, protonation, and subsequent single electron oxidation to afford the key alkyl carbocation intermediate. This protocol exhibits advantages of broad functional group tolerance, excellent atom economy, high efficiency, and mild reaction conditions.

Photocatalytic Decarboxylative Fluoroalkylation of α,β‐Unsaturated Carboxylic Acids

A decarboxylative fluoroalkylation of α,β‐unsaturated acids was developed by the use of a dual nickel/photoredox catalysis system. The fluoroalkyl radicals are generated from α‐CF3 alkyl bromides by nickel‐induced single electron transfer (SET) and are subsequently intercepted by a cinnamic acid to forge the targeted C‐C bonds. A wide variety of substrates bearing a diverse set of functional groups were compatible with the mild reaction conditions (visible light, room temperature, cheap metal, no strong oxidant or reductant), thus affording trifluoromethyl analogues of α‐methylated allylic compounds.

Photocatalyzed Arylthiolation/Cyclization of 3‐(2‐(Ethynyl)phenyl)Quinazolinones with Disulfides towards Arylthiolated Quinolino[2,1‐b]Quinazolinones

AbstractAn approach to the synthesis of arylthiolated quinolino[2,1‐b]quinazolinones has been developed using unactivated alkynes containing quinazolinones and diaryldisulfides under visible light irradiation. The procedure entails a sequential radical arylthiolation and cyclization reaction. A possible radical mechanism has been investigated and proven as a single electron transfer (SET) process.

Photodetectors performance of nanostructured materials in antimony III-V InGaAsSb/AlGaAsSb interband cascade structures

The aim of the study is to increase the performance of solar conversion by integrating nanostructured materials within conventional solar cells by employing multi-energy stages (i.e., interband and intersubband) in cascade systems to overcome the absorption length barrier and achieve large photo-generated carrier values. Specifically, InGaAsSb/Al GaAsSb MQWs are investigated with narrow well widths (2-20 nm) and transition energies of the structures are calculated for varied well/barrier widths and depths using numerical modelling. The results show that both interband and intersubband transitions are valuable for improving photovoltaic and photodetection applications, but their mechanisms and applications are distinct, so understanding and controlling these transitions within semiconductor materials is essential for optimising the performance of devices in both areas of optoelectronics, including strain as an important parameter of integrity. The data suggests that a single electron requires multiple photons to be transported, with the formation of a type-I broken-gap alignment between AlGa AsSb (barrier) and InGaAsSb (well). A wide range of wavelengths, from visible to medium infrared (MIR), will greatly enhance solar spectrum absorption. The long-term goal is to combine the thermal properties of antimonies (GaSbInSb) with a low band gap and the optical properties of arsenide (GaAsAlAs) with a large band gap.

Advances in Light Promoted Transformation of N-Heterocyclic Carbene-Ligated Boryl Radical

Organoboron compounds are integral to modern life, with extensive applications in synthesis, materials science, medicine, and various other domains closely linked to human endeavors. NHC-BH3, noted for its stability, ease of synthesis, and high reactivity as a boryl radical precursor, has emerged as a key focus in boryl radical chemistry. Recently, the visible-light-induced single electron transfer (SET) and hydrogen atom transfer (HAT) processes have garnered considerable interest, presenting innovative strategies for generating boryl radicals from NHC-BH3. In the context of this review, our focus is on the synthesis of C-B and X-B bonds under visible light irradiation, facilitated by NHC-BH3. Furthermore, we explored the role of NHC-BH3 as a hydrogen donor or halogen atom transfer reagent in the construction of C-C bond.

Asymmetric Synthesis of Dialkyl Carbinols by Ni-Catalyzed Reductive-Oxidative Relay of Distinct Alkenes.

Enantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic properties of two alkyl substituents. Herein, an unprecedented synthesis of chiral dialkyl carbinol ester derivatives from Ni-catalyzed reductive-oxidative relay cross-coupling of two alkenes is developed for the first time. The reaction features the use of enol esters and unactivated alkenes as two different alkyl equivalents to undergo head-to-tail and enantioselective alkyl-alkyl cross-coupling. The reaction undergoes two-electron reduction and single electron oxidation in the presence of both reductants and oxidants. The use of an allyl bromide as single electron acceptor is crucial for the success of this non-trivial asymmetric cross-coupling, providing a new reaction mode for asymmetric alkyl-alkyl bond-forming event in the absence of stoichiometric alkyl electrophiles.

Induced magnetic effects on intrinsic properties of edge-passivated triangular zigzag phosphorene quantum dots using spin-polarized density functional theory

The electrical and magnetic characteristics of edge-passivated triangular zigzag phosphorene quantum dots, saturated with hydrogen and oxygen atoms, have been investigated using spin-polarized density functional theory. The findings indicate that oxygen passivation alters the bond lengths, cohesive energies, and bandgaps of the quantum dots, leading to increased stability and magnetism due to unbonded single electrons in the oxygen atoms. The study also explored the impact of an external electric field on the energy gap, molecular orbital distribution, and local spin density of selected quantum dots. Our results show significant changes in the energy spectra and magnetic moments of the magnetized structures. The tunability of the magnetic and electronic attributes of triangular phosphorene quantum dots can be exploited in designing electronic and spintronic devices.