Electron Donor Research Articles

Tuning the Spin State of Co Accelerates Hydrogen Evolution Reaction of Pt Nanoparticles

ABSTRACTThe quest for dynamic and cost‐effective electrocatalysts to substitute carbon‐supported platinum (Pt) in alkaline hydrogen evolution reaction (HER) remains a pressing challenge. The incorporation of transition metal atoms through electron donation and spin regulation dominates the HER performance of Pt nanoparticles. Herein, we demonstrate that Co‐N coordination was utilized to regulate and stabilize the chemical microenvironment of Pt nanoparticles to fabricate hybrid electrocatalysts (Pt/CoNC). The resultant Pt/CoNC delivers ultralow overpotentials of 15.2 and 171.2 mV at current densities of 10 and 100 mA cm−2, surpassing commercial Pt/C. The poisoning tests, where η10 values of Pt/CoNC depict negative shifts of 161 and 13 mV by potassium thiocyanide (KSCN) and ethylenediaminetetraacetic acid disodium (EDTA), suggest the combined impact of Pt nanoparticles and Co‐N coordination on HER, with Pt nanoparticles playing a decisive role. The magnetic characterization and spin density diagrams reveal that Pt induces a higher spin state of Co2+, creating a wider spin‐related channel for electron donation to Pt. Moreover, Co‐N effectively modifies the electronic structure of Pt, thereby reducing the energy barriers for H2O dissociation (from 0.41 to −0.22 eV) and H2 generation (from −0.35 to 0.03 eV). This finding provides insights to fabricate advanced electrocatalysts through regulating spin state and modulating interfacial electron transfer.

Panchromatic Absorption of Unsymmetrical Donor-Acceptor Dyes Based on a Meta-conjugated 1,3,5-Heteroaryltriazine Core.

Attachment of three different heterocycles with electron donor or acceptor character to a central 1,3,5-triazine core generates readily soluble side-chain free dyes with two displaying soft crystalline mesomorphism and one displaying a nematic liquid crystal phase as confirmed by polarized optical microscopy, calorimetry, gravimetric analysis, and powder X-ray diffraction. Equally intriguing is the dyes' relatively strong electronic communication between donor and acceptor subchromophores that are meta-conjugated to one another, which is experimentally observed as a broad intramolecular charge-transfer absorption that can extend over 100 nm past the most intense absorption event and is computationally confirmed through density functional theory (DFT) evaluations of the molecular ground- and excited-state properties. This molecular design permits the preparation of dyes with panchromatic absorption not just based on the additive absorption of individual subchromophores.

Enhancing corrosion resistance in HCl environments: Comparative efficacy of a conjugated 3ph-Schiff base versus benzotriazole

This research addresses the need for effective corrosion inhibitors in industrial applications, evaluating the performance of 4-nitro-2-(((1E,2E)-3-phenylallylidene)amino)aniline (noted as 3ph-Schiff base) as a corrosion inhibitor in comparison to benzotriazole (BTA) in a high-concentration 3 M HCl environment. Unlike studies conducted in lower concentrations (e.g. 0.1 and 1 M), this study aims to assess inhibitor performance under more aggressive conditions. Rigorous methods, including Tafel polarisation, electrochemical impedance spectroscopy (EIS), and mass loss measurements, revealed variations in inhibition efficiency (IE). Polarisation data indicated that 3ph-Schiff base at 0.3% (approximately 8.96 mM) achieved a maximum IE of 99.5%, surpassing BTA at the same concentration (approximately 25.2 mM), which recorded an IE of 96.9%. Meanwhile, EIS analysis yielded slightly lower IE values, with 3ph-Schiff base reaching 90.21% and BTA 67.39%, reflecting the complementary nature of these methods. The corrosion inhibition mechanism of 3ph-Schiff base is attributed to strong adsorption on the metal surface, where amino (NH2) and nitro (NO2) groups promote stable complex formation with metal ions, enhancing electron donation and forming a protective layer that blocks corrosive agents. Scanning electron microscopy and elemental mapping confirm uniform nitrogen and carbon surface coverage, integral to the protective layer. This layer acts as both a physical barrier and an electrochemical passivator, effectively reducing anodic and cathodic reactions. The combined effects of adsorption, physical blocking and passivation underscore the 3ph-Schiff base's superior performance as a corrosion inhibitor in acidic environments.

Ammonia Decomposition Catalyzed by Co Nanoparticles Encapsulated in Rare Earth Oxide.

We fabricated Co-based catalysts by the low-temperature thermal decomposition of R-Co intermetallics (R = Y, La, or Ce) to reduce the temperature of ammonia cracking for hydrogen production. The catalysts synthesized are nanocomposites of Co/ROx with a metal-rich composition. In the Co13/LaO1.5 catalyst derived from LaCo13, Co nanoparticles of 10-30 nm size are enclosed by the LaO1.5 matrix. The nanocomposite exhibited superior catalytic activity (91% at 500 °C), which was attributed to dual advantages; the low workfunction of the supporter, O-deficient LaO1.5-x nanoparticles, promotes electron donation to the Co catalyst in the interface, which leads to enhanced N-H bond dissociation. Moreover, such a composite structure is effective in suppressing the grain growth of Co nanoparticles because the LaO1.5 layer works as a diffusion barrier against Co. The thermal decomposition of intermetallics is a new route for the facile synthesis of catalysts having an electronically active support.

Hot-Exciton Mechanism with Diphenyl Anthracene Core Unit: A Detailed Theoretical Study.

Hot-exciton materials, among all kinds of organic light-emitting diode (OLED) emitters, have better exciton utilization efficiency and efficiency roll-off, making them possible for their practical applications. We studied the photophysical properties of a few hot-exciton molecules based on an anthracene core unit to efficiently harvest all triplet excitons to the lowest excited singlet state. The conversion of triplet exciton to singlet exciton utilizing hRISC can be enhanced due to the 1ππ*←3nπ* transition channel. The energy gap between the excited singlet and triplet excited states, spin-orbit coupling interaction, nature of excited states, rate constants of reverse intersystem crossing, and radiative process were calculated and analyzed to gain more insights into the hot-exciton mechanism. Additionally, we extended our study by substituting groups in the diphenyl anthracene core unit to find improved performance. We found that the combinations of triphenylamine (TPA) or 9-phenyl-9H-carbazole (CZP) acting as the electron donor, benzophenone as the acceptor, and the anthracene as the π-bridge is the most efficient hot-exciton emitter for improved OLED lighting application technology.

A metal-organic framework with mixed electron donor and electron acceptor ligands for efficient lithium-ion storage.

Electron donor tetrathiafulvalene (TTF) and electron acceptor naphthalene diimide (NDI) derivatives were used to synthesize a 3D Zn-TTF/NDI-MOF. Multiple redox active sites and charge transfer endow the pristine MOF anode with excellent rate behavior and long term cycling performance (with an average specific capacity of 956 mA h g-1 at 1 A g-1 over 600 cycles). This study highlights the great potential of elaborately-designed MOFs for developing efficient anode materials.

Superconductivity of electron-doped chalcohydrides under high pressure

As a typical representative of covalent superconductors, SH3 has emerged as a significant milestone in superconductivity history and has greatly sparked interest in compressed hydrogen-rich superconductors. Authors of previous studies on theoretical design of ternary chalcogen-hydrogen compounds (known as chalcohydrides) have mainly focused on intercalating molecular motifs into the interstitial sites of the structural lattice or substituting atoms in the SH3 backbone. Given the low electronegativity and small radius, lithium (Li) is empowered to serve as an excellent electron donor that can effectively turn the crystal structure and modulate the superconducting behavior. Here, we introduce Li into binary chalcohydrides and investigate ternary Li-M-H (M = S, Se, and Te) compounds using the state-of-the-art structure prediction method in conjunction with first-principles calculations. As a result, five stable stoichiometries, including LiSH7, Li2SH6, LiSH, Li2SH, and LiS2H, are identified at 100–200 GPa. Notably, metallic LiSH7 and Li2SH6 exhibit a layered structure where the covalent bond between sulfur and hydrogen breaks up and the hydrogen atoms are released to recombine into molecules confined into the interlayer. Furthermore, our electron-phonon simulations reveal that the estimated superconducting transition temperature (Tc) of Li2SH6 (46 K) is lower than that (77 K) of Li2SeH6 at 200 GPa, which contrasts with the general belief that the light-weight elemental compound (high Debye temperature) has higher superconductivity. Our results offer critical insights into designing high-temperature superconductors with layered structures among multinary hydrides. Published by the American Physical Society 2025

A Native LH1–RC–HiPIP Supercomplex from an Extremophilic Phototroph

Halorhodospira (Hlr.) halophila strain BN9622 is an extremely halophilic and alkaliphilic purple phototrophic bacterium and has been widely used as a model for exploring the osmoadaptive and photosynthetic strategies employed by phototrophic extreme halophiles that enable them to thrive in hypersaline environments. Here we present the cryo-EM structures of (1) a unique native Hlr. halophila triple-complex formed from light-harvesting (LH1), the reaction center (RC), and high-potential iron–sulfur protein (HiPIP) at 2.44 Å resolution, and (2) a HiPIP-free LH1–RC complex at 2.64 Å resolution. Differing from the LH1 in the Hlr. halophila LH1–LH2 co-complex where LH1 encircles LH2, the RC-associated LH1 complex consists of 16 (rather than 18) αβ-subunits circularly surrounding the RC. These distinct forms of LH1 indicate that the number of subunits in a Hlr. halophila LH1 complex is flexible and its size is a function of the photocomplex it encircles. Like LH1 in the LH1–LH2 co-complex, the RC-associated LH1 complex also contained two forms of αβ-polypeptides and both dimeric and monomeric molecules of bacteriochlorophyll a. The majority of the isolated Hlr. halophila LH1–RC complexes contained the electron donor HiPIP bound to the surface of the RC cytochrome subunit near the heme-1 group. The bound HiPIP consisted of an N-terminal functional domain and a long C-terminal extension firmly attached to the cytochrome subunit. Despite overall highly negative surface-charge distributions for both the cytochrome subunit and HiPIP, the interface between the two proteins was relatively uncharged and neutral, forming a pathway for electron tunneling. The structure of the Hlr. halophila LH1–RC–HiPIP complex provides insights into the mechanism of light energy acquisition coupled with a long-distance electron donating process toward the charge separation site in a multi-extremophilic phototroph.

Machine Learning Assisted Bithiophene Based Donor Acceptor Selection to Design New Fluoresent Dyes for Photovoltaic Applications.

This study investigates the electronic properties and photovoltaic (PV) performance of newly designed bithiophene-based dyes, focusing on their light harvesting efficiency (LHE), open-circuit voltage (Voc), fill factor (FF), and short-circuit current density (Jsc).These new dyes are designed with the help of machine learning (ML) to design best donor acceptor designs. For this, we collect 2567 differenr electron donor groups and calculated their bandgap with the help of Random Forest (RF) Regression method. Their maximum absorption (λmax) values are redshifted with their 367-501nm range having TA1 with higher value. Their LHE values range from 52 to 89%, with TA3 demonstrating the highest efficiency. Their Voc values varies significantly, with TA2 achieving the highest at 1.584V, while TA5 and TA6 exhibit lowest values. Their FF)from 25.9 for TA4 to 59.3 for TA3, highlighting the superior charge extraction capabilities. Their Jsc values further reflect their performance potential, with TA1 leading at 39.43mA/cm², while TA4 and TA6 show significantly lower values of 3.28 and 4.40mA/cm², respectively. Overall, the findings suggest that the bithiophene-based dyes, particularly TA2 and TA3, possess promising characteristics for enhancing the efficiency of solar cells.

Synergistic transformation of Cr(VI) in lubricant degradation by bacterial consortium.

In recent years, it has become widely acknowledged that heavy metals are often present in oil-contaminated sites. This study utilized three specific types of microorganisms with different functions to construct a composite bacterial consortium for treating lubricant-Cr(VI) composite pollutants. The selected strains were Lysinbacillus fusiformis and Bacillus tropicus. The Back Propagation Neural Network-genetic algorithm was employed to optimize the secondary bacterial addition time to 67h and the strain ratio to 2:1. The optimized process involved the use of 4.6g/L glucose and ammonium oxalate as electron donors. After 6 days of treatment with the composite consortium, the removal rates of 1500mg/L lubricating oil and 50mg/L chromium reached 90.3% and 84.2%, respectively. Initial analysis using three-dimensional fluorescence to examine the changes in extracellular polymers in the bacteria when exposed to chromium-lubricating oil, showed that 30mg/L Cr(VI) could induce the secretion of extracellular protein-like substances. These substances may be directly or indirectly involved in the biological detoxification mechanism of chromium. The synergistic removal of complex pollutants has the potential to transform previous "unilateral" removal studies and enhance bioremediation efficiency.

Phytochemical and Antioxidant Analysis of Bioactive Compound Extract from Nelumbo nucifera against Cancer Proteins: In Silico Spectroscopic Approach.

Nelumbo nucifera, an aquatic crop cultivated throughout Asian countries, belongs to the Nelumbonaceae family and has been widely used in traditional medicines with key pharmacological activities such as anti-viral, antipyretic, antioxidant, anti-steroid, anti-inflammatory, anti-arrhythmia, anti-obesity, and anti-aging properties. The present study aims to explore and assess the phytochemical composition, GC-MS profiling, antioxidant efficacy, and the major phytoconstituent phytol subjected to theoretical spectroscopic characterization using the DFT method. The phytochemical profiling of N. nucifera reveals the presence of alkaloids, carbohydrates, saponin, phenol, and flavonoids. The antioxidant efficacy of N. nucifera extract against DPPH and ABTS radicals increased in a concentration-dependent manner, with an IC50 value of 222.84µg and 52.67µg, respectively. The simulated structural parameters of phytol exhibited strong concordance with experimental values. The simulated wavenumbers identified characteristic peaks corresponding to hydroxyl (OH), methylene (CH2), and methyl (CH3) groups. The simulated electronic spectrum of phytol exhibits a prominent absorption peak at 174nm, predominantly attributed to the transitions H-1 → L (58%) and H → L (36%). NBO analysis reveals significant stabilization energy (7.09kJ/mol) due to the donation of electrons from the C20-H58 bonding orbital to the anti-bonding orbital of C18-C19 via a σ → σ* transition. In Mulliken charge distribution, compared to other hydrogen, hydrogen H61 in the hydroxyl (O-H) group exhibits a higher positive potential due to the influence of the oxygen atom. In addition, molecular docking was performed against breast cancer SMAD proteins to confirm its antagonist property, with binding energies of - 3.64kcal/mol (6OM2), - 5.49kcal/mol (1U7F), - 5.05kcal/mol (1U7V), and - 3.73kcal/mol (6FX4).

Advanced Dual-Mode Microfluidic Sensing Platform Based on Amphiphilic Polymer-Capped Perovskite Nanozymes Induced Photoelectrochemical Signal Amplification and Fluorescence Emission.

A novel dual-mode microfluidic sensing platform integrating photoelectrochemical (PEC) and fluorescence (FL) sensors was developed for the sensitive monitoring of heart fatty acid binding protein (h-FABP). First, BiVO4/AgInS2 (BVAIS) composites with excellent photoelectric activity were synthesized as sensing matrices. The BVAIS heterojunction with a well-matched internal energy level structure provided a stable photocurrent. Second, an innovative signal amplification strategy based on octylamine-modified poly(acrylic acid) (OPA)-capped CsPbBr3 (OPCB) nanocrystals (NCs) with excellent catalytic activity and fluorescence property was proposed. On the OPCB nanozyme possessing ascorbate oxidase-like catalytic activity could catalyze the oxidation of ascorbic acid, which achieved quenching of the photocurrent signals by competitively consuming the electron donor. On the other hand, the OPCB NCs that overcame the water stability defect processed good luminescence performance and were able to produce obvious FL signals. Mutually verified dual-response signals effectively enhance the precision of test outcomes and avoid false-positive or false-negative results. Finally, the constructed microfluidic sensing platform realized sensitive detection of h-FABP in the linear range of 0.0001-150 ng/mL (PEC mode) and 0.001-150 ng/mL (FL mode), with detection limits of 36 fg/mL and 0.32 pg/mL, respectively. The present work provided a new perspective for designing an efficient dual-mode sensing strategy to achieve sensitive detection of disease markers.

Differential diversity and structure of autotrophs in agricultural soils of Qinghai Province.

Agricultural soil plays important roles in carbon fixation during carbon capture and storage. Autotrophic bacteria that utilize inorganic compounds as electron donors for growth fix CO2 photosynthetically or chemo-autotrophically in diverse ecosystems and affect soil organic carbon sequestration. Soil properties, agronomic management measures, and environmental factors can influence the community composition, abundance, and activity of CO2-assimilating bacteria. This study aims at evaluating the effects of different regions and crop types on the abundance, composition, and activity of CO2-fixing bacteria in agricultural soil.

Carbon Defects as Highly Active Sites for Gold Detection and Recovery.

The use of precious metals (PMs) in many areas, such as printed circuit boards, catalysts, and target drugs, is increasing due to their unique physical and chemical properties, but their recovery remains a great challenge in terms of zero-valent PMs as the final product. We report a highly hydrophilic carbon dot (CD) as a reductant (electron donor), in which the defects in CD served as efficient active sites for zero-valent PMs recovery with an electron-donating capacity of ~1.7 mmol g-1. The reduction of gold follows a two-step dynamic model characterized by the formation of nano-gold nuclei (initial rapid electron transfer process) followed by an Ostwald ripening process (subsequent slow process). Finite element method (FEM) simulation shows that the reaction efficiency and confinement effect of AuCl4 - ions are positively correlated with defect density, indicating that the quantitative control of carbon defect density is the key to enhancing reduction activity. Combining density functional theory (DFT) with XPS and FTIR technology, we found that the electron is transferred from CD to Au(III) via hydrogen bonding. This nano carbon material can be exploited to recover gold from e-waste water directly, with the characteristics of reducing energy consumption and avoiding environmental pollution.

Peroxiredoxin 6 maintains mitochondrial homeostasis and promotes tumor progression through ROS/JNK/p38 MAPK signaling pathway in multiple myeloma

Peroxiredoxin 6 (PRDX6) is one of the Peroxiredoxin family members with only 1-Cys, using glutathione as the electron donor to reduce peroxides in cells. PRDX6 has been frequently studied and its expression was associated with poor prognosis in many tumors. However, the expression of PRDX6 in multiple myeloma (MM) and its relevance with MM remain unclear. In our study, we found that PRDX6 was overexpressed in MM patients. Its high expression was inversely correlated with prognosis but positively correlated with the levels of β2-microglobulin (B2M), lactate dehydrogenase (LDH), and International Staging System (ISS) stage of MM patients. Further, the deficiency of PRDX6 promoted MM cell lines (RPMI 8226, MM.1S, and U266) apoptosis significantly. Mechanically, PRDX6 serves as an anti-oxidative enzyme, and its deficiency led to over-accumulation of reactive oxygen species (ROS), resulting in oxidative stress, following the activation of MAPK signaling pathway, which manifested as phosphorylation of JNK and p38. Then, the expression of BAX and Bcl2 was imbalance, and the cascade cleavage of PARP and caspase 3 was increased, ultimately triggering cell apoptosis. In addition, oxidative stress decreased mitochondrial membrane potential (MMP), reduced gene expression levels of oxidative phosphorylation (OXPHOS), and increased in the density of mitochondrial crumpling, leading to mitochondrial structural abnormalities and dysfunction. Furthermore, PRDX6 deficiency combined with bortezomib induced a robust anti-tumor effect in MM cell lines. Finally, in vivo experiments also showed that the deficiency of PRDX6 inhibited tumor growth of tumor-bearing mice. Collectively, PRDX6 protects MM cells from oxidative damage and maintains mitochondrial homeostasis. And targeting PRDX6 is an attractive strategy to enhance the anti-tumor effect of bortezomib in MM.

Phanerochaete chrysosporium hyphae bio-crack, endocytose and metabolize plastic films.

Numerous studies have focused on the effect and mechanism of plastic degradation; due to their high persistence, petroleum-based plastics are difficult for microbes to mineralize. Although such plastics have been demonstrated to be mineralized by white rot fungus, the reactions at the molecular level remain unknown. Here, we show the whole mineralization model of polyethylene film, that can be summarized as follows: 1) white rot fungus colonizes on polyethylene film, using additives as dissimilated carbon sources; 2) the fungus secretes extracellular enzymes protein, combining with stearic acid as electron donor, causes oxidation and cracking of polyethylene film; and 3) partial dissociated sub-microplastic debris access to cells, further oxidizes in sequential actions of intracellular enzymes, and ultimately mineralize via β-oxidation. Our study provides new insight into the causes of polyethylene film cracking degradation model.

Recent advances in synthetic biology toolkits and metabolic engineering of Ralstonia eutropha H16 for production of value-added chemicals.

Ralstonia eutropha H16, a facultative chemolithoautotrophic Gram-negative bacterium, demonstrates remarkable metabolic flexibility by utilizing either diverse organic substrates or CO2 as the sole carbon source, with H2 serving as the electron donor under aerobic conditions. The capacity of carbon and energy metabolism of R. eutropha H16 enabled development of synthetic biology technologies and strategies to engineer its metabolism for biosynthesis of value-added chemicals. This review firstly outlines the development of synthetic biology tools tailored for R. eutropha H16, including construction of expression vectors, regulatory elements, and transformation techniques. The availability of comprehensive omics data (i.e., transcriptomic, proteomic, and metabolomic) combined with the fully annotated genome sequence provides a robust genetic framework for advanced metabolic engineering. These advancements facilitate efficient reprogramming metabolic network of R. eutropha. The potential of R. eutropha as a versatile microbial platform for industrial biotechnology is further underscored by its ability to utilize a wide range of carbon sources for the production of value-added chemicals through both autotrophic and heterotrophic pathways. The integration of state-of-the-art genetic and genomic engineering tools and strategies with high cell-density fermentation processes enables engineered R. eutropha as promising microbial cell factories for optimizing carbon fluxes and expanding the portfolio of bio-based products.

Understanding charge separation in CdS/Ce-UiO66-NH2 heterojunctions for enhanced photocatalytic hydrogen evolution

The enhanced H2 evolution efficiency of the CdS/Ce-UiO-NH2 heterojunction is attributed to its ability to generate long-lived (ms) charges. In contrast with Zr-UiOs, Ce-UiO-NH2 acts as the electron donor in this heterojunction.

An ultra-sensitive photoelectrochemical sensor based on ZnIn2S4/rGO nanocomposites for detection of oxytetracycline in water, food and organism samples

Residues of oxytetracycline (OTC) may cause the resistance of bacteria, and even have serious impacts on the ecosystem through the food chain. It was important to monitor OTC of low concentration for preserving human health and environmental safety. In this work, reduced graphene oxide doped ZnIn2S4 (ZnIn2S4/rGO) nanocomposites were composited by straightforward one-step solvothermal reaction. The nanocomposites had superior light absorption property and stable photocurrent response. Because rGO not only had a large specific surface area for immobilizing abundant ZnIn2S4, but also accelerated charge transfer as an electron mediator. Additionally, the oxidation potential of OTC was more negative than the valence band potential of ZnIn2S4. So, OTC can be oxidized by photogenerated holes of the ZnIn2S4 as electron donors, leading significant increase of photocurrent response. Based on this, a “signal-on” photoelectrochemical (PEC) sensor was constructed to achieve ultra-sensitive and specific detection of OTC. This sensor exhibited a wide detection range from 100 fM to 50 nM, an extremely low detection limit (61.2 fM) and excellent analytical performance in actual water, food and biological samples.

Stabilizing 4π electron pyrrolyl cations by inducing aromaticity.

The pyrrolyl cation is a 4π electron ring system which is anti-aromatic and unstable. This work reports an experimental procedure to obtain stable pyrrolyl cations. Electron donation from N-heterocyclic carbenes makes the ring stable by converting a 4π electron ring system into a 6π electron ring system.