Direct Transfer Research Articles

Electroredox N-Heterocyclic Carbene-Catalyzed Enantioselective (3 + 3) Annulation of Enals with 2-Naphthols.

Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants. The mechanistic studies and cyclic voltammetry suggest that the reaction proceeds via direct single electron transfer (SET) of the in situ-generated Breslow intermediate.

Synergistic Promotion of Direct Interspecies Electron Transfer by Biochar and Fe₃O₄ Nanoparticles to Enhance Methanogenesis in Anaerobic Digestion of Vegetable Waste

When vegetable waste (VW) is used as a sole substrate for anaerobic digestion (AD), the rapid accumulation of volatile fatty acids (VFAs) can impede interspecies electron transfer (IET), resulting in a relatively low biogas production rate. In this study, Chinese cabbage and cabbage were selected as the VW substrates, and four continuous stirred tank reactors (CSTRs) were employed. Different concentrations of biochar-loaded nano-Fe3O4(Fe3O4@BC) (100 mg/L, 200 mg/L, 300 mg/L) were added, and the organic loading rate (OLR) was gradually increased during the AD process. The changes in biogas production rate, VFAs, and microbial community structure in the fermentation tanks were analyzed to identify the optimal dosage of Fe3O4@BC and the maximum OLR. The results indicated that at the maximum OLR of 3.715 g (VS)/L·d, the addition of 200 mg/L of Fe3O4@BC most effectively promoted an increase in the biogas production rate and reduced the accumulation of VFAs compared to the other treatments. Under these conditions, the biogas production rate reached 0.658 L/g (VS). Furthermore, the addition of Fe3O4@BC enhanced both the diversity and abundance of bacteria and archaea. At the genus level, the abundance of Christensenellaceae_R-7_group, Sphaerochaeta, and the archaeal genus Thermovirga was notably increased.

Multi-agent Reinforcement Learning for the Control of Three-Dimensional Rayleigh–Bénard Convection

AbstractDeep reinforcement learning (DRL) has found application in numerous use-cases pertaining to flow control. Multi-agent RL (MARL), a variant of DRL, has shown to be more effective than single-agent RL in controlling flows exhibiting locality and translational invariance. We present, for the first time, an implementation of MARL-based control of three-dimensional Rayleigh–Bénard convection (RBC). Control is executed by modifying the temperature distribution along the bottom wall divided into multiple control segments, each of which acts as an independent agent. Two regimes of RBC are considered at Rayleigh numbers $$\textrm{Ra}=500$$ Ra = 500 and 750. Evaluation of the learned control policy reveals a reduction in convection intensity by $$23.5\%$$ 23.5 % and $$8.7\%$$ 8.7 % at $$\textrm{Ra}=500$$ Ra = 500 and 750, respectively. The MARL controller converts irregularly shaped convective patterns to regular straight rolls with lower convection that resemble flow in a relatively more stable regime. We draw comparisons with proportional control at both $$\textrm{Ra}$$ Ra and show that MARL is able to outperform the proportional controller. The learned control strategy is complex, featuring different non-linear segment-wise actuator delays and actuation magnitudes. We also perform successful evaluations on a larger domain than used for training, demonstrating that the invariant property of MARL allows direct transfer of the learnt policy.

112 Effect of electrical field during thawing of in vitro-produced bovine embryos cryopreserved for direct transfer

112 Effect of electrical field during thawing of in vitro-produced bovine embryos cryopreserved for direct transfer

Transition Metal Chalcogenides/Nonconjugated Polymer Artificial Photosystems for Photoredox Catalysis.

Surface charge transfer doping (SCTD) has been established as an efficient strategy to achieve strong electronic coupling interactions between semiconductors and dopants, which lead to highly efficient electron transport over semiconductors. Herein, we report a facile, easily accessible, and effective SCTD strategy to exquisitely modulate the interfacial charge transfer over transition metal chalcogenides (TMCs: CdS, Zn0.5Cd0.5S, CdIn2S4, and ZnIn2S4) through surface modification with a nonconjugated polymer, poly(dimethyldiallylammonium chloride) (PDDA). We provide evidence that PDDA, as a surface electron transfer acceptor, can be used to enable rapid, directional, and tunable charge transfer along with an optimal charge lifetime over TMCs in photoredox catalysis because of the high-efficiency electron-trapping property of quaternary ammonium functional groups in the molecular structure of PDDA. The thus-assembled PDDA-encapsulated TMC composite artificial photosystems demonstrate significantly enhanced and versatile photoredox catalytic activities toward visible-light-responsive photocatalytic reduction of aromatic nitro compounds, photocatalytic oxidation of aromatic alcohols, and photocatalytic H2 production, wherein the ultrathin PDDA layer accelerates the interfacial charge transport and separation rate over TMC substrates. Moreover, it was evidenced that such an interface engineering strategy is general for a collection of TMCs. Our work will provide conceptual insights into nonconjugated polymer-based artificial photosystems for optimizing solar energy utilization.

Response of Metabolic Gene Panel to Organic Loading Stress in Propionate-Degrading Methanogenic Anaerobic Digesters

Propionate, a critical intermediate in anaerobic digestion, and its syntrophic removal, is sensitive to stress. To our knowledge, this study investigates for the first time the response of a metabolic gene panel to organic loading rate (OLR) stress in propionate-degrading methanogenic consortia in lab-scale upflow anaerobic sludge blanket (UASB) reactors. The experimental phases included stabilisation (1.4–2.8 g COD/L/day), electroactive enrichment, OLR shock (6 g COD/L/day), and early recovery. Quantitative PCR was used to assess the abundance of key functional genes (16SrRNA, mcrA, pilA, and hgtR). During stabilisation, ~200 mLCH₄/h was produced, the mcrA/16SrRNA ratio was 0.78–2.64, and pilA and hgtR abundances were 1.29–2.27 × 105 and 2.12–4.37 × 104 copies/gVS. Following the OLR shock, methane production ceased entirely, accompanied by a sharp decline in the mcrA/16S ratio (0.08–0.24) and significant reductions in pilA (1.43-log) and hgtR (1.34-log) abundance. Partial recovery of pilA and hgtR abundance (1.19 × 105 and 8.57 × 104) was observed in the control reactor after the early recovery phase. The results highlight the utility of mcrA, 16SrRNA, pilA, and associated ratios, as reliable indicators of OLR stress in lab-scale UASB reactors. This study advances the understanding of molecular stress responses in propionate-degrading methanogenic consortia, focusing on direct interspecies electron transfer in process stability and recovery.

Agrarian Reform and Land for Youth?: Responding to Agricultural Gerontocracy among Palm Sugar Farmers in the Menoreh Mountains

This paper aims to examine the contribution of agrarian reform in addressing the gerontocracy of agriculture in rural areas. The research specifically focuses on examining how the post-agrarian reform program in Gunung Kukusan hamlet has shifted land ownership and control from the older to the younger generation, and how agrarian reform has influenced changes in land management control. The research was conducted using a qualitative approach. Data collection techniques included in-depth interviews, observation, and documentation. Data analysis was carried out qualitatively by categorizing and visualizing the data. The research results clearly demonstrate the issue of agricultural gerontocracy, particularly the tendency to view agricultural activities as a secondary profession. Agrarian reform through asset restructuring and access restructuring does not bring about changes in land control, ownership, and management. Land certification serves as a confirmation of ownership rather than a direct transfer of ownership. The practice of land grabbing shows that management control is entirely in the hands of landowners, most of whom belong to the older generation. The youth lack the authority to make changes to the generations-old coconut farming practices. This situation underscores the need for agrarian reform policies that accommodate the issue of youth landlessness.

Covalent Organic Frameworks for Boosting H2O2 Photosynthesis via the Synergy of Multiple Charge Transfer Channels and Polarized Field

AbstractCovalent organic frameworks (COFs) serve as one of the most promising candidates for hydrogen peroxide (H2O2) photosynthesis, while attaining high‐performance COFs remains a formidable challenge due to the insufficient separation of photogenerated charges. Here, through the rational design of bicarbazole‐based COFs (Cz‐COFs), we showcase the first achievement in piezo‐photocatalytic synthesis of H2O2 using COFs. Noteworthily, the ethenyl group‐modified Cz‐COFs (COF‐DH‐Eth) demonstrates a record‐high yield of H2O2 (9212 μmol g−1 h−1) from air and pure water through piezo‐photocatalysis, which is ca. 2.5 times higher than that of pristine Cz‐COFs without ethenyl groups (COF‐DH‐H) under identical condition and COF‐DH‐Eth without ultrasonic treatment. The H2O2 production rate originates from the synergistic effect between an ultrasonication‐induced polarized electric field and the spatially separated multiple charge transfer channels, which significantly promote the utilization of photogenerated electrons by directional transfer from bicarbazole groups to the ethenyl group‐modified benzene rings. Several Cz‐COFs and bifluorenylidene‐based COFs (COF‐BFTB‐H) with similar twisted monomers exhibit obvious piezoelectric performance for promoting H2O2 generation, signifying that organic ligands with a twistable structure play a crucial role in creating broken symmetry structures, thereby establishing piezoelectric properties in COFs.

Co-occurrence of direct and indirect extracellular electron transfer mechanisms during electroactive respiration in a dissimilatory sulfate reducing bacterium.

Understanding the extracellular electron transfer mechanisms of electroactive bacteria could help determine their potential in microbial fuel cells (MFCs) and their microbial syntrophy with redox-active minerals in natural environments. However, the mechanisms of extracellular electron transfer to electrodes by sulfate-reducing bacteria (SRB) remain underexplored. Here, we utilized double-chamber MFCs with carbon cloth electrodes to investigate the extracellular electron transfer mechanisms of Desulfovibrio vulgaris Hildenborough (DvH), a model SRB, under varying lactate and sulfate concentrations using different DvH mutants. Our MFC setup indicated that DvH can harvest electrons from lactate at the anode and transfer them to cathode, where DvH could further utilize these electrons. Patterns in current production compared with variations of electron donor/acceptor ratios in the anode and cathode suggested that attachment of DvH to the electrode and biofilm density were critical for effective electricity generation. Electron microscopy analysis of DvH biofilms indicated DvH utilized filaments that resemble pili to attach to electrodes and facilitate extracellular electron transfer from cell to cell and to the electrode. Proteomics profiling indicated that DvH adapted to electroactive respiration by presenting more pili- and flagellar-related proteins. The mutant with a deletion of the major pilus-producing gene yielded less voltage and far less attachment to both anodic and catholic electrodes, suggesting the importance of pili in extracellular electron transfer. The mutant with a deficiency in biofilm formation, however, did not eliminate current production indicating the existence of indirect extracellular electron transfer. Untargeted metabolomics profiling showed flavin-based metabolites, potential electron shuttles.IMPORTANCEWe explored the application of Desulfovibrio vulgaris Hildenborough in microbial fuel cells (MFCs) and investigated its potential extracellular electron transfer (EET) mechanism. We also conducted untargeted proteomics and metabolomics profiling, offering insights into how DvH adapts metabolically to different electron donors and acceptors. An understanding of the EET mechanism and metabolic flexibility of DvH holds promise for future uses including bioremediation or enhancing efficacy in MFCs for wastewater treatment applications.

The optimization of phase change heat transfer model for direct contact condensation heat transfer simulation based on Bayesian inversion method

Direct contact condensation heat transfer between steam and water is widely applied across various industries. The utilization of phase change models significantly influences the precision of numerical simulation outcomes in this domain. This study presents numerical simulations of direct contact condensation between steam and liquid films generated by nozzles. Employing Bayesian inversion method, this research conducts optimizations on the Lee and Schrage models and examines the impact of varying treatments of interface area density. Additionally, it proposes enhancements to these methodologies. The findings of this study are expected to foster a more profound comprehension of phase change models and their role in numerical simulations.

B-UMCS: Blockchain-enabled Unified Medical Consultancy Service.

The advent of blockchain technology within the healthcare domain has signified a paradigm shift, transitioning from an emerging trend to an essential infrastructure component that ensures decentralization, transparency, integrity, and persistent availability. Despite its potential, the healthcare sector has not fully capitalized on the vast array of benefits blockchain technology offers. Most existing works utilized blockchain technology within a specific healthcare entity's services but not among several healthcare organizations. They notably lack the provision for direct communication and knowledge transfer between doctors from different hospitals. Therefore, this paper introduces a pioneering Blockchain-based Unified Medical Consultancy Service (B-UMCS) that leverages blockchain's robustness to revolutionize telehealth services by (a) alleviating the shortage of medical expertise through facilitating the interconnection of physicians from diverse hospitals and geographical areas onto a consolidated platform, (b) promoting the seamless sharing of medical consultations, electronic health records (EHRs), and expert insights while upholding rigorous security and privacy protocols, (c) integrating the inherent security mechanisms of blockchain with the distributed data storage functionality offered by the Interplanetary File System (IPFS). This work details the B-UMCS's components, interactions, smart contracts, protocols, algorithms, storage and transmission of EHRs, and their corresponding implementations. The evaluations of the proposed B-UMCS reveal that it secures and facilitates the sharing of EHRs and enables healthcare professionals to collaborate and exchange expertise seamlessly across institutional boundaries. They are additionally ensuring that healthcare providers can offer their knowledge in an efficient and scalable manner. Overall, B-UMCS not only addresses the current challenges in healthcare data security and accessibility but also opens new avenues for collaboration and knowledge sharing among healthcare professionals, ultimately contributing to improving patient care quality.

Curbing Leakage in Public Programs: Evidence from India’s Direct Benefit Transfer Policy

Targeted price subsidies create a gap between subsidized and unsubsidized prices. The resulting dual pricing can lead to arbitrage opportunities where intermediaries divert subsidized goods to unintended beneficiaries via the black market. I study India’s Direct Benefit Transfer policy for cooking fuel subsidies, which altered the existing subsidy program by transferring subsidies directly to beneficiaries’ bank accounts. The policy decreased subsidized fuel purchases, indicating a reduction in diversion to the black market. Changes in unsubsidized fuel sales and black market prices provide supporting evidence that leakage was reduced. These results suggest that addressing the underlying perverse incentives in welfare delivery can improve efficiency by curbing leakages. (JEL D73, I38, O17, Q41, Q48)

Phosphorous Incorporated PtNi Networks with Synergistic Directional Electron Transfer for Efficient and Durable Seawater Hydrogen Production

AbstractThe abundant chloride ions in seawater, which poison and corrode electrode materials, are the main reason for the low performance of Pt‐based catalysts toward hydrogen evolution reaction (HER) in seawater. Coupling Pt with oxophilic transition metals can enhance the activity of Pt‐based electrocatalysts, but their long‐term stability is still unsatisfactory. Herein, a small number of phosphorous atoms (from 1.2 to 5.9 at%) are precisely incorporated into PtNi networks (P‐PtNi networks) via a facile aqueous reduction strategy at room temperature. Experimental measurements and theoretical calculations prove that P incorporation leads to a synergistic directional electron transfer from P and Ni to Pt, resulting in improved water dissociation kinetics, enhanced Cl– resistance and facilitated hydrogen adsorption. Consequently, P‐PtNi networks exhibit outstanding HER activities with a lower overpotential of 37 mV at 10 mA cm−2 and an 8.5‐fold higher mass activity at –0.07 V compared to commercial Pt/C and only slightly lowered potential after 120 h of testing in alkaline simulated seawater. Furthermore, P‐PtNi networks show an ultrahigh solar‐to‐hydrogen efficiency of 15.2% for solar cell‐driven hydrogen production from seawater. This work sheds new lights on the design of high‐performance Pt‐based nanomaterials toward practical applications of seawater hydrogen production.

Highly effective catalytic degradation of bisphenol a through activation of peroxymonosulfate by an Fe-Nx structure anchored on novel lignin-based graphitic biochar: Electron transfer mechanism

A lignin-based Fe/N co-doped carbonaceous catalyst was synthesized via freeze-drying followed by pyrolysis to activate peroxymonosulfate (PMS) for efficient degradation of bisphenol A (BPA). The Fe/N co-doped biochar exhibited a high specific surface area (364.84 m2/g), hierarchical porous structures, and abundant oxygen-containing functional groups (hydroxyl and carboxyl groups), which enhancing the dispersion of Fe3O4 nanoparticle and exposure of catalytic site. The Fe8-N10-C/PMS system achieved 100 % BPA degradation within 20 min with a corresponding first-order reaction rate constant (kobs) of 0.4056 min−1, which outperformed most reported catalysts in efficiency. Quenching and EPR analyses revealed that both free radicals (•OH, SO4•−, and O2•−) and non-radical (1O2) were rate-limiting steps, while graphitic N and Fe-Nx structures facilitated direct electron transfer from BPA to PMS in electrochemical tests. XPS results confirmed that pyrrolic N, rather than pyridinic N, played a crucial role in forming the Fe-Nx structure. Moreover, the catalyst showed excellent stability, regeneration capability, and adaptability under diverse conditions, highlighting the potential of the Fe-N-C/PMS system for practical wastewater treatment applications.

Graphite-enhanced methanogenesis in coal measure shale anaerobic digestion: Implications for increasing gas yield and CO2 utilization

Anaerobic digestion (AD) of coal measure shale (CMS) for methane production is a promising technology for increasing yield of coal measure gas (CMG) wells. However, improving methane production efficiency of CMS remains a challenge. Conductive material has been shown to promote biogas production in different AD systems, but its effectiveness in CMS requires investigation. In this study, graphite was selected as conductive material due to its low cost and suitability for field applications, and its effects on methane production was investigated. The results indicate that as graphite concentration increases from 0 to 1.6 g/L, the methane production of CMS increases. However, when the graphite concentration reaches 2.0 g/L, the methanogenesis is inhibited, resulting in lower methane production compared to the control group. In the group with a graphite concentration of 1.6 g/L, the abundances of Romboutsia and Pseudomonas increase, which improves the compatibility of the microbial community with the CMS AD system and causes the amount of the substrates for methanogenesis to increase. Also, the direct interspecies electron transfer between Methanobacterium, Methanosaeta and Pseudomonas is strengthened, which enhances the methane production. However, excessive addition of graphite (2.0 g/L) intensifies the competitions from dissimilatory iron reduction and sulfate reduction reactions for substrates and electrons with the methanogenesis, causing the methane production to decrease. This study confirms the effectiveness of graphite in enhancing methane production of CMS, and the promoted hydrogenotrophic methanogenesis enhances the CO2 methanation, which offers an efficient pathway for increasing CMG well yield and enabling CO2 underground utilization.

Impaired brainstem auditory evoked potentials after in utero exposure to high dose paracetamol exposure

Paracetamol is an analgesic and antipyretic medication regarded as the safest over-the-counter pain and fever relief option during pregnancy. Paracetamol and its metabolites are known to reach the developing fetus through direct placental transfer and can cross the blood brain barrier. Several recent, large-scale epidemiologic studies suggest that in utero paracetamol exposure can increase the risk of neurodevelopmental conditions, including autism spectrum disorder (ASD), attention deficit hyperactivity disorder (ADHD) and developmental delay (DD). Since auditory processing deficits are a common feature of ASD, we hypothesized that animals exposed to paracetamol in utero will have impaired auditory brainstem function. We investigated this hypothesis by recording and analyzing click-evoked auditory brainstem responses (ABR) at postnatal day 21 and 29 in Sprague-Dawley rats. In utero exposure to high dose paracetamol exposure had no impact on body or brain weight. However, high dose paracetamol exposure did significantly delay ear opening and resulted in elevated ABR thresholds, and longer wave and interwave latencies. These changes in wave latency extended to the highest click intensity tested but were most severe near threshold. This data suggests that development and function of the auditory brainstem may be impacted by high dose paracetamol exposure and that simple, non-invasive tests of auditory function have utility as an early screening tool for neurodevelopmental disorders.

Oxygen vacancies-rich BiOBr bridged direct electron transfer with peroxymonosulfate for integrating superoxide radical and singlet oxygen on selective pollutants degradation

Oxygen vacancies-rich BiOBr bridged direct electron transfer with peroxymonosulfate for integrating superoxide radical and singlet oxygen on selective pollutants degradation

Pediatric Esophageal Button Battery Protocol Reduces Time From Presentation to Removal.

Evaluate implementation of an institutional protocol to reduce the time to removal of esophageal button battery (BB) and increase use of mitigation strategies. We developed a protocol for esophageal BB management [Zakai's Protocol (ZP)]. All cases of esophageal BB impaction managed at a tertiary care center before and after implementation from 2011 to 2023 were reviewed. Time to BB removal, adherence to critical steps, and use of mitigation strategies (honey/sucralfate, acetic acid) were evaluated. Fifty-one patients (38 pre-ZP, 13 post-ZP) were included. Median age was 2.3 years (IQR 1.3-3.4). After implementation, the time from arrival at the institution to arrival in the operating room (OR) reduced by 4.2 h [4.6 h (IQR 3.9-6.5) to 0.4 h (IQR 0.3-0.6), p < 0.001] and there was improvement in all management steps. The number of referrals direct to otolaryngology increased from 51% to 92%, arrival notification increased from 86% to 100%, avoidance of second x-ray increased from 63% to 100%, and direct transfer to OR increased from 92% to 100%. Adherence to mitigation strategies such as preoperative administration of honey or sucralfate increased from 0% to 38%, intraoperative use of acetic acid from 3% to 77%, and nasogastric tube insertion from 53% to 92%. Implementation of ZP substantially reduced the time to BB removal and the use of mitigation strategies in our tertiary care institution. Additional strategies focused on prevention of BB ingestion, and shortening the transfer time to the tertiary care hospital are required to prevent erosive complications. 3, Case-series Laryngoscope, 134:5170-5177, 2024.

Vehicle-to-Grid Power Transfer Method for Electric Vehicles using off-board charger

This article explores a power transfer technique from vehicle to grid (V2G) via the construction of an off-board charger for electric cars (EVs). The charger accommodates several charging modes, such as grid-to-vehicle (G2V), vehicle-to-vehicle (V2V), and vehicle-to-grid (V2G), facilitating efficient and adaptable energy management. In G2V mode, the charger utilizes grid power to recharge electric vehicle batteries, whilst V2V mode enables direct energy transfer between electric vehicles, circumventing the grid. The novel integration of G2V and V2V modes enables the concurrent use of grid electricity and energy from other electric vehicles, therefore diminishing grid reliance and enhancing power efficiency. The system has a three-phase pulse width modulation (PWM) rectifier that sustains a constant DC link voltage and attains a unity power factor on the grid side, therefore adhering to the IEEE 519 standard for total harmonic distortion (THD). Furthermore, a half-bridge bidirectional DC/DC converter guarantees consistent charging and discharging currents, hence improving the reliability and efficiency of the charging process. This holistic strategy enhances dynamic energy flow and grid stability while providing possible economic advantages to electric vehicle owners and operators via the integration of renewable energy sources and sophisticated management algorithms for improved energy use and storage.

Automated optimisation design of barge structures using integrated knowledge-based approaches

ABSTRACT An integrated automatic optimisation simulation system for barge structure design has been developed to enhance efficiency and quality. This system incorporates a knowledge-based geometrical modelling method for barge structure design, allowing for the automatic construction of computational models of barge sections through direct transfer of geometric models. Furthermore, a barge structure optimisation simulation system integrated with direct calculation has been established. The effectiveness of this approach is demonstrated through the successful application of structural optimisation to a 65 m barge section, resulting in higher quality design solutions. This research offers an efficient and effective method for achieving high-quality design solutions in the field of barge structure design.