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The interactions between π-systems in dimers of aromatic molecules lead to particularly stable conformations within the relative orientations of the monomers. Extensive research has been conducted on the properties of these complexes in the neutral state. However, in recent decades, there has been a significant surge in applications harnessing these structures for electrical purposes. Therefore, this study places particular emphasis on a deeper understanding of the redox properties of these compounds and how to modify them. To achieve this, we have focused on modeling the effect of a wide range of functional groups on the redox properties of benzene derivatives, observing a correlation between these properties and the change in the molecular dipole moment. Then, we investigated the effect of π-stacking interactions on these properties in dimers formed by either identical or different monomers. In both cases, there is an enhancement of the reducing character of the systems due to these interactions. Upon oxidation, the charge is distributed proportionally to the redox potential of each monomer. Therefore, if there is heterogeneity in these potentials, the properties of the complete cationic system will be influenced by the monomer with a greater tendency to undergo oxidation. The considered models serve as an excellent example for studying the behavior of nucleobases in DNA or aromatic amino acids, among others. [ABSTRACT FROM AUTHOR]

Redox potentials depend on the nature of the solvent/electrolyte through the solvation energies of the ionic solute species. For concentrated electrolytes, ion solvation may deviate significantly from the Born model predictions due to ion pairing and correlation effects. Recently, Ghorai and Matyushov [J. Phys. Chem. B 124, 3754–3769 (2020)] predicted, on the basis of linear response theory, an anomalous trend in the solvation energies of room temperature ionic liquids, with deviations of hundreds of kJ/mol from the Born model for certain size solutes/ions. In this work, we computationally evaluate ionic solvation energies in the prototypical ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM/BF4), to further explore this behavior and benchmark several of the approximations utilized in the solvation energy predictions. For comparison, we additionally compute solvation energies within acetonitrile and molten NaCl salt to illustrate the limiting behavior of purely dipolar and ionic solvents. We find that the overscreening effect, which results from the inherent charge oscillations of the ionic liquid, is substantially reduced in magnitude due to screening from the dipoles of the molecular ions. Therefore, for the molten NaCl salt, for which the ions do not have permanent dipoles, modulation of ionic solvation energies from the overscreening effect is most significant. The conclusion is that ionic liquids do indeed exhibit unique solvation behavior due to peak(s) in the electrical susceptibility caused by the ion shell structure; redox potential shifts for BMIM/BF4 are of more modest order ∼0.1 V, but may be larger for other ionic liquids that approach molten salt behavior. [ABSTRACT FROM AUTHOR]

Taking into account the electron-rich and visible light response of thiophene, first-principles calculations have been carried out to explore the photocatalytic activity of donor–acceptor polymers incorporating thiophene and boron. Honeycomb-kagome boron–thiophene (BTP) polymers with varying numbers of thiophene units and fixed B center atoms are direct bandgap semiconductors with tunable bandgaps ranging from 2.41 to 1.88 eV and show high absorption coefficients under the ultraviolet and visible regions of the solar spectrum. Fine-tuning the band edges of the BTP polymer is efficiently achieved by adjusting the pore size through the manipulation of thiophene units between the B centers. This manipulation, achieved without excessive chemical functionalization, facilitates the generation of an appropriate quantity of photoexcited electrons and/or holes to straddle the redox potential of the water. Our study demonstrates that two units between B centers of thiophene in BTP polymers enable overall photocatalytic water splitting, whereas BTP polymers with larger pores solely promote photocatalytic hydrogen reduction. Moreover, the thermodynamics of hydrogen and oxygen reduction reactions either proceed spontaneously or need small additional external biases. Our findings provide the rationale for designing metal-free and single-material polymer photocatalysts based on thiophene, specifically for achieving efficient overall water splitting. [ABSTRACT FROM AUTHOR]

Electrochemical and photochemical hydrogen (H2) evolution activities of a 6-fluoro-2-hydroxypyridinate (fhp−)-bridged paddlewheel-type dirhodium (Rh2) complex, [Rh2(fhp)4], were investigated through experimental and theoretical approaches. In DMF, the [Rh2(fhp)4] underwent a one-electron reduction (assigned to Rh24+/3+) at −1.31 V vs SCE in the cathodic region. Adding trifluoroacetic acid as a proton source to the electrochemical cell containing [Rh2(fhp)4], the significant catalytic current, i.e., electrochemical H2 evolution, was observed; the turnover frequency and overpotential of electrochemical H2 evolution were 18 244 s−1 and 732 mV, respectively. The reaction mechanism of electrochemical H2 evolution catalyzed by [Rh2(fhp)4] in DMF was examined in detail by theoretically predicting the redox potentials and pKa values of the reaction intermediates using density functional theory calculations. The calculations revealed that (i) the formation of a one-electron reduced species, [Rh2(fhp)4]−, triggered for H2 evolution and (ii) the protonation and reduction processes of [Rh2(fhp)4]− to further reduced hydride intermediates proceeded directly via a concerted proton–electron transfer mechanism. Moreover, [Rh2(fhp)4] was shown to be a highly efficient H2 evolution catalyst (HEC) for photochemical proton reduction reactions when combined with an artificial photosynthetic (AP) system containing [Ir(ppy)2(dtbbpy)]PF6 and triethylamine, which served as a photosensitizer and a sacrificial electron donor, respectively. Under visible light irradiation, the total amount of H2 evolved and its turnover number (per Rh ion) were 1361.0 µmol and 13 610, respectively, which are superior to those of previously reported AP systems with rhodium complexes as HEC. [ABSTRACT FROM AUTHOR]

A poly(ionic liquid) probe material was prepared that is conductive, uniformly film-forming, and rich in I2 interaction sites by structural design. Green and pollution-free electrochemical detection of gaseous I2 was achieved based on the variation of redox peak currents, and the limit of detection was 1.44 nM. The differences in redox peak potentials were utilized for the specific detection of gaseous I2. [ABSTRACT FROM AUTHOR]

The widespread adoption of rechargeable alkaline batteries is plagued by the performance‐limiting metal anodes, which are prone to (electro)chemical corrosion and raise environmental or economic concerns. Organic redox‐active materials offer a potential solution, but they typically struggle with dissolution‐induced degradation and insufficiently negative reduction potentials. Herein, we introduce benzo[c]cinnoline and its derivatives (collectively referred to as BCCs), a class of aromatic azo compounds with fused‐ring structure, as promising organic anode materials. BCCs exhibit pronounced aromaticity and Brønsted basicity, conferring low reduction potentials and intrinsic insolubility in alkaline solutions. Paired with the industrially established nickel hydroxide cathode, these batteries deliver excellent capacity (297 mAh g−1anode), high output voltage of 1.3 V, and extended cycle life (≈16000 cycles). Notably, they also operate efficiently at extremely low temperatures down to −85 °C with an 8 M KOH electrolyte. We further explore the feasibility for all‐organic alkaline batteries by paring BCCs with the dihydro form of 4,4’‐azopyridine, utilizing azo compounds for both anode and cathodes. This chemistry harnesses the unique properties of small organic molecules to enable all‐organic batteries with high capacity of 236 mAh g–1, fast charging at 1200 C, and easy recyclability. [ABSTRACT FROM AUTHOR]

Singly‐linked aromatic [22]smaragdyrin BF2 complex dimer was synthesized by the reductive coupling of 16‐brominated [22]smaragdyrin BF2 complex, which was oxidized to a stable diradical with PbO2. As the first example of fused smaragdyrin dimer, a fused [22]smaragdyrin BF2 complex dimer was synthesized by the oxidation of a CuCl‐BF2 complex dimer with FeCl3 and subsequent reduction with NaBH4. After removal of the BF2 group, the singly‐linked and fused aromatic dimers were oxidized to the corresponding antiaromatic [20]smaragdyrin free base dimers. The first oxidation and reduction potentials of these dimers are split depending upon the intramolecular electronic interactions, which are larger for the fused dimers. Despite the large electronic interactions, the aromatic and antiaromatic characters are well preserved in the fused dimers. [ABSTRACT FROM AUTHOR]

Metallic zinc has emerged as a promising anode material for high‐energy battery systems due to its high theoretical capacity (820 mAh g−1), low redox potential for two‐electron reactions, cost‐effectiveness and inherent safety. However, current zinc metal batteries face challenges in low coulombic efficiency and limited longevity due to uncontrollable dendrite growth, the corrosive hydrogen evolution reaction (HER) and decomposition of the aqueous ZnSO4 electrolyte. Here, we report an interfacial‐engineering approach to mitigate dendrite growth and reduce corrosive reactions through the design of ultrathin selective membranes coated on the zinc anodes. The submicron‐thick membranes derived from polymers of intrinsic microporosity (PIMs), featuring pores with tunable interconnectivity, facilitate regulated transport of Zn2+‐ions, thereby promoting a uniform plating/stripping process. Benefiting from the protection by PIM membranes, zinc symmetric cells deliver a stable cycling performance over 1500 h at 1 mA/cm2 with a capacity of 0.5 mAh while full cells with NaMnO2 cathode operate stably at 1 A g−1 over 300 cycles without capacity decay. Our work represents a new strategy of preparing multi‐functional membranes that can advance the development of safe and stable zinc metal batteries. [ABSTRACT FROM AUTHOR]

Objectives: This study discusses the experience at our centre with treating traumatic thoracolumbar fractures using percutaneous pedicle screw fixation. Methods: We reviewed the case notes and imaging retrospectively between January 2013 and June 2019. Results: A total of 257 patients were included, 123 males and 134 females aged between 17 and 70; the mean age was 47.6 years. The majority of injuries were from fall from significant height. The fractures involved the thoracic and lumbar vertebra in 98 and 151 of the cases respectively. Percutaneous pedicle screw fixation was performed either one or two levels above and below the fracture depending on the level of injury. Forty two cases were treated with additional short pedicle screws at the level of fracture. More than 15% (39) of the patients presented with a neurological deficit; more than 80% (32) of those showed post-operative improvement in their neurology as per Frankel Grading system. The mean operative time was 117 min ± 45 min; mean length of hospital stay was 7.2 days ± 3.8 days, with significant improvement in pain. Conclusions: Percutaneous pedicle screw fixation is a safe surgical option with comparable outcomes to open surgery and a potential reduction in perioperative morbidity. [ABSTRACT FROM AUTHOR]

Bi‐reforming hydrogen production has its potential in the reduction of greenhouse gas emissions. In this work, methane bi‐reforming process in a packed bed reactor using bi‐disperse catalyst particles is numerically investigated via a particle‐resolved modeling. The impacts of macropore fraction, porosity and macropore size on temperature and reaction rate distribution in the bed are evaluated. The results demonstrate that there exists a peak of the maximum temperature difference in the bed with the catalyst macropore fraction. Increasing the macropore fraction of the catalyst can weaken the non‐uniformity of coke formation in the bed. The increase in the macropore size of the catalyst particle can promote the hydrogen production, especially when the macropore size of particle is smaller. [ABSTRACT FROM AUTHOR]

• A new method for comprehensively evaluating GHG emissions from HFWC-MSW landfills. • HFWC and LFWC MSW have greatly different time distributions of GHG emissions. • Method for assessing unmonitored fugitive LFG emissions. • Collecting LFG in advance is essential for reducing GHG emissions with HFWC MSW. • HFWC-MSW landfills have great GHG emissions reduction potentials. This study proposes a comprehensive evaluation method based on a two-stage model to assess greenhouse gas (GHG) emissions and reductions in high-food-waste-content (HFWC) municipal solid waste (MSW) landfills. The proposed method considers typical processes such as fugitive landfill gas (LFG), LFG collection, flaring, power generation, and leachate treatment. A case study of an HFWC MSW landfill in eastern China is considered to illustrate the evaluation. The findings revealed that the GHG emissions equivalent of the case landfill amounted to 21.23 million tons from 2007 to 2022, averaging 1.03 tons CO 2 -eq per ton of MSW. There was a potential underestimation of LFG generation at the landfill site during the initial stages, which led to delayed LFG collection and substantial fugitive LFG emissions. Additionally, the time distribution of GHG emissions from HFWC MSW was significantly different from that of low-food-waste-content (LFWC) MSW landfills, with peak emissions occurring much earlier. Owing to the rapid degradation characteristics of HFWC MSW, the cumulative LFG production of the landfill by 2022 (2 years after the final cover) was projected to reach 77 % of the total LFG potential. In contrast, it would take until 2030 for LFWC MSW landfills to reach this level. Furthermore, various scenarios were analyzed, in which if the rapid LFG generation characteristics of HFWC MSW are known in advance, and relevant facilities are constructed ahead of time, the collection efficiency can be improved from 31 % to over 78 %, resulting in less GHG emissions. [ABSTRACT FROM AUTHOR]

Sn x P y particles are in-situ encapsulated into MXene conductive networks by hydrothermal and phosphorization processes as novel anode materials of the sodium ion battery. MXene amounts and hydrothermal durations were investigated to evenly distribute Sn x P y in MXene. [Display omitted] • Sn x P y particles are in-situ encapsulated into MXene conductive network (Sn x P y /MXene). • MXene ratio and hydrothermal duration is studied to evenly distribute Sn x P y in MXene. • Sn x P y /MXene has capacities of 438.8 and 314.1 mAh/g at 0.2 and 1.0 A/g, respectively. • Capacity retentions of 6.0 % and 73.6 % are respectively got for Sn x P y and Sn x P y /MXene. • Sn x P y has smaller volume expansion and MXene self-stacking is reduced in Sn x P y /MXene. Sodium-ion battery (SIB) is one of potential alternatives to lithium-ion battery, because of abundant resources and lower price of sodium. High electrical conductivity and long-term durability of MXene are advantageous as the anode material of SIB, but low energy density restricts applications. Tin phosphide possesses high theoretical capacity, low redox potential, and large energy density, but volume expansion reduces its cycling stability. In this study, tin phosphide particles are in-situ encapsulated into MXene conductive networks (Sn x P y /MXene) by hydrothermal and phosphorization processes as novel anode materials of SIB. MXene amounts and hydrothermal durations are investigated to evenly distribute Sn x P y in MXene. After 100 cycles, Sn x P y /MXene reaches high specific capacities of 438.8 and 314.1 mAh/g at 0.2 and 1.0 A/g, respectively. The capacity retentions of 6.0% and 73.6% at 0.2 A/g are respectively obtained by Sn x P y and Sn x P y /MXene. The better specific capacity and cycling stability of Sn x P y /MXene are attributed to less volume expansion of Sn x P y during charge/discharge processes and relieved self-stacking of MXene by encapsulating Sn x P y particles between MXene layers. Electrochemical impedance spectroscopy and Galvanostatic intermittent titration technique are also applied to analyze the charge storage mechanism in SIB. Higher sodium ion diffusion coefficient and smaller charge-transfer resistance are obtained by Sn x P y /MXene. [ABSTRACT FROM AUTHOR]

[Display omitted] The lack of compactness in heterojunction interfaces and poor charge separation is a great challenge in developing high-efficiency heterojunction photocatalysts. Herein, a novel Bi 4 Ti 3 O 12 -BiPO 4 heterojunction was successfully prepared for the first time by epitaxial growth of BiPO 4 on the surface of Bi 4 Ti 3 O 12 nanosheets. The optimized Bi 4 Ti 3 O 12 -BiPO 4 -0.5 increased the NO oxidation efficiency to 73.05%, surpassing pure Bi 4 Ti 3 O 12 (63.45%) and BiPO 4 (8.35%). Experiments and theoretical calculations indicated that the closely contacted heterointerface between BTO and BPO promoted the generation of the built-in electric field, which led to the formation of the Z- scheme transfer pathway for the photogenerated carriers. Therefore, the separation of photogenerated carriers was facilitated while retaining high redox potential, generating more ·O 2 – and ·OH to participate in NO oxidation. Furthermore, the adsorption of NO and O 2 was enhanced by introducing BiPO 4 , further improving the photocatalytic NO oxidation performance. This work emphasizes the critical role of heterointerface in accelerating charge transfer, providing a basis for the design and construction of tightly contacted heterojunction photocatalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • The results of theoretical prediction guide the system design and preparation. • NFS@MCS shows enhanced full solar spectrum-driven photocatalytic H 2 evolution. • The photothermal effect of NFS boosts the H 2 evolution reaction. • The S-scheme heterojunction mechanism and formation of IEF was proposed. In addition to the intrinsic driving force of photocatalysis, the external thermal field from the photothermal effect can provide additional energy to the photo-catalytic system to improve the photo-catalytic hydrogen-evolution (PHE) efficiency. Herein, based on the results of density functional theory, we designed and constructed a hollow core–shell FeNi 2 S 4 @Mn 0.3 Cd 0.7 S (NFS@MCS) S-scheme heterojunction with a photothermal effect, thereby realising a significant enhancement of the PHE performance due to the thermal effect, S-scheme heterojunction and hollow core–shell morphology. As a light collector and heat source, the hollow NFS could absorb and convert photons into heat, resulting in the increased local temperature of photocatalyst particles. Moreover, the S-scheme charge path at the interface not only improved the carrier separation efficiency but also retained a higher redox potential. All these are favourable to increase the PHE activity. The PHE tests show that 0.5 %-NFS@MCS exhibits the highest PHE rate of 17.11 mmol·g−1·h−1, 7.7 times that of MCS. Moreover, through a combination of theoretical calculation and experimental evidence, the PHE mechanism of the NFS@MCS system is discussed and clarified in-depth. [ABSTRACT FROM AUTHOR]

BACKGROUND AND OBJECTIVES: Newborns, particularly premature ones, are vulnerable to bacterial infections and often receive antibiotics, disrupting their normal intestinal microbiota. Probiotics have multiple health benefits and are recommended for restoring balance, but caution is needed due to potential consequences, such as promoting antibiotic resistance. Therefore, this study aimed to conduct a systematic review to assess current knowledge regarding the impact of probiotics on antibiotic resistance in newborns. METHODS: This systematic review is aligned with the PRISMA 2020 statement. The search involved three electronic databases (PubMed, Scopus, and Web of Science) and the keywords used were "newborn", "probiotic", and "antibiotic resistance". Titles/abstracts were independently analyzed, followed by full-text assessments. Data extraction and synthesis were conducted, assessing outcomes like antibiotic resistance gene and mobile gene elements quantity and quality, vancomycin resistant enterococci colonization, antibiotic-resistant bacteria colonization, and microbiota changes. It was only included randomized controlled trials and cohort studies focusing on human newborns. RESULTS: In the study selection process, 1,970 articles were identified and six were included in this review. The results varied, with two studies suggesting a positive impact of probiotics on antibiotic resistance, one a negative impact, while three others found no significant impact. Microbiota changes were also addressed across four studies, where the findings included promotion of beneficial bacteria and reduction of potential pathogens. Bias risk was evaluated using Joanna Briggs Institute tools. CONCLUSION: Our findings did not allow for clear conclusions to be drawn, due to the observed heterogeneity between studies, highlighting the need for further studies. [ABSTRACT FROM AUTHOR]

Purpose: This study developed new measures of the routine and non-routine task contents of managerial, professional, technical, and clerical occupations from a workload perspective. Here, we present a comparative analysis of the workload structures of state and industrial sector employees. Design/methodology/approach: Our method involves detailed descriptions of work processes and an element-wise time study. We collected and analysed data to obtain a workload structure that falls within three conceptual task categories: (i) non-routine analytic tasks, (ii) non-routine interactive tasks and (iii) routine cognitive tasks. A total of 2,312 state and industrial sector employees in Kazakhstan participated in the study. The data were collected using a proprietary web application that resembles a timesheet. Findings: The study results are consistent with the general trend reported by previous studies: the higher the job level, the lower the occupation's routine task content. In addition, the routine cognitive task contents of managerial, professional, technical, and clerical occupations in the industrial sector are higher than those in local governments. The work of women is also more routinary than that of men. Finally, vthe routine cognitive task contents of occupations in administrative units are higher than those of occupations in substantive units. Originality/value: Our study sought to address the challenges of using the task-based approach associated with measuring tasks by introducing a new measurement framework. The main advantage of our task measures is a direct approach to assessing workloads consisting of routine tasks, which allows for an accurate estimation of potential staff reductions due to the automation of work processes. [ABSTRACT FROM AUTHOR]

The present work intended to produce new cost-effective alkali-activated adsorbents from chestnut shells with the purpose of removing fluoride from water, and to explore the effect of pyrolysis temperature on fluoride decontamination at different operational and environmental parameters. The microstructure and morphological characteristics of the resulting activated carbons were thoroughly investigated using BET, FTIR, XRD and SEM. The effectiveness of the prepared adsorbent materials in treating and remediating fluorinated water was evaluated. The impacts of several factors, including the dose of the adsorbent, the initial contamination level of fluoride, and pH on the fluoride removal efficiency were investigated. In accordance with the data, the highest adsorption was found to be at a 6 pH during 5 hours of processing duration and 0.5 g/L of dosage of adsorbent. The experimental results were well-fit by the Freundlich isotherm model and the pseudo-second-order kinetic model. The highest fluoride removal efficiency was found to be 78% at adsorption medium pH 6 and initial fluoride concentration of 10 mg/L by the adsorbent prepared at 800°C. Additional research on adsorption along with rejuvenation revealed that the reduction in adsorption potential to 10% following four repetitions of operation involving regeneration, thereby showcasing the adsorbent's versatile applicability for repeated use. [ABSTRACT FROM AUTHOR]

Solid organ transplantation continues to be the only or most efficient therapeutic solution for several end-stage diseases. The success of such transplantation is largely dependent on the swift transportation of organs from donors to recipients, as Cold Ischemia Time (CIT) plays a critical role in determining the recipient's medical outcome. This study explores the potential of Advanced Air Mobility (AAM) in the context of organ transplantation in Austria and Germany. AAM, in the healthcare sector, is associated with potential overall process time savings via air transportation, thereby reducing CIT. However, the application of AAM for organ transplantation has not yet been implemented in Europe. This study employs a Monte Carlo simulation to derive the trip length distributions for organ transplantation in Austria and Germany. By utilizing data from Eurotransplant (2018–2021) and ÖBIG (2017–2021), it was found that 48% of organ transports within Germany, and 80% of organ transports within Austria, fall within a trip length of less than 150 km. This distance is within the capabilities of today's AAM technology. Anticipated time benefits of up to 30 min compared to ground-based transport can be expected. Furthermore, the optimization of the organ transport process, facilitated by AAM, promises greater potential for CIT reduction. [ABSTRACT FROM AUTHOR]

Protective coatings for Zn anode are developed to suppress Zn dendrite growth, inhibit hydrogen evolution reaction (HER), and provide good anti‐corrosion properties. However, preparing protective coatings with all three of these characteristics remains a challenge. In this study, a triple‐functional amorphous In2O3 protective layer for Zn anodes is designed. The high redox potential of In/In3+ ensures the stability of the coating in aqueous electrolytes and effectively suppresses HER. Theoretical calculations indicate that the amorphous In₂O₃ protective layer has high Zn2⁺ affinity, which lowers the nucleation barrier for Zn2⁺ and suppresses dendrite growth. Furthermore, the anisotropy of this amorphous material provides homogeneous Zn2+ adsorption sites and enhances corrosion resistance. Consequently, amorphous In2O3@Zn symmetric batteries have excellent stability and a cycle life far exceeding that of bare Zn, showing the ability to undergo continuous stripping/plating at 1 mA cm−2 for >5400 h. At a current density of 10 A g−1, an amorphous In2O3@Zn//Ca‐V2O5 full cell retains a specific capacity of 307.3 mA h g−1 after 5000 cycles (cycle retention: 76%). The successful preparation of In2O3@Zn provides a new approach for obtaining highly stable and long‐life Zn anodes. [ABSTRACT FROM AUTHOR]

Bidentate N‐ligands are paramount to recent advances in nickel‐catalyzed cross‐coupling reactions. Through comprehensive organometallic, spectroscopic, and computational studies on bi‐oxazoline and imidazoline ligands, we reveal that a square planar geometry enables redox activity of these ligands in stabilizing nickel radical species. This finding contrasts with the prior assumption that bi‐oxazoline lacks redox activity due to strong mesomeric donation. Moreover, we conducted systematic cyclic voltammetry (CV) analyses of bidentate pyridyl, oxazoline, and imidazoline nitrogen ligands, along with their corresponding nickel complexes. Complexation with nickel shifts the reduction potentials to a more positive region and narrows the differences in redox potentials among the ligands. Additionally, various ligands led to different degrees of bromide dissociation from singly reduced (L)Ni(Ar)(Br) complexes, reflecting varying reactivity in the subsequent activation of alkyl halides, a crucial step in cross‐electrophile coupling. These insights highlight the significant electronic effects of ligands on the stability of metalloradical species and their redox potentials, which interplay with coordination geometry. Quantifying the electron‐donating, π‐accepting properties of these ligands, as well as their effect on catalyst speciation, provides crucial benchmarks for controlling catalytic activity and enhancing catalyst stability. [ABSTRACT FROM AUTHOR]

Owing to the crustal abundance of sodium element, sodium ion batteries (SIBs) are considered a promising complementary to lithium‐ion battery for stationary energy storage applications. The cointercalation chemistry enables the use of cost‐effective graphite as anodes, whereas the low capacity (<130 mAh g−1) and high redox potential (>0.6 V vs. Na/Na+) of graphite significantly limit the energy density of SIBs. Herein, we induce the high‐capacity Na metal into sodiophilic ternary graphite intercalation compounds (t‐GICs) via co‐intercalation and deposition reactions, thereby achieving Na/t‐GIC anodes with high capacities and low working voltage (0.18 V). The new anodes exhibit high coulombic efficiencies of above 99.7 % over 550 cycles and a high‐rate capacity of 588.4 mAh g−1 at 6 C (10 min per charge). When it is paired with Na3V2(PO4)2F3 (NVPF) cathodes, the SIBs demonstrate a high energy density of 259 Wh kg−1both electrodes surpassing that of commercial LiFePO4//graphite batteries. The outstanding anode performance is attributed to the tailored sodiophilicity of graphite through manipulating the ether solvents and the in situ generated space among t‐GIC flakes to stably accommodate Na metal. Our findings for stable Na plating/striping on sodiophilic graphite materials provide an effective approach for developing advanced SIBs. [ABSTRACT FROM AUTHOR]

The emerging high entropy oxide (HEO) with homogenously distributed multicomponent featuring great adjustability of composition and electronic structure shows attractive electrocatalyst performance. Herein, the SO 4 2--modified (Fe 0.2 Co 0.2 Ni 0.2 Cr 0.2 Mn 0.2) 3 O 4 grown on the hollow carbon sphere (HCS) has been prepared using a microwave-solvothermal strategy. The introduction of thioacetamide during the formation of HEO leads to the in-situ generation of SO 4 2− on the surface of HEO, which not only drives surface morphology and crystal structure evolution to expose more electrochemical active sites, but also intensifies surface reconstruction, including the formation of more hypervalent active metal ions, and the reduction of the reconstruction potential, thus improving the catalytic activity. The amorphous high-entropy structure with unsaturated coordination encourages more active sites generation. The HCS carriers effectively disperse the HEOs and promote gas release and electron transfer. As a return, the SO 4 2--modified HEO/HCS shows decreased charge transfer impedance and improved electrochemical active surface areas. The catalyst with the optimal S content exhibits a low overpotential of 237 mV at 10 mA cm−2 and Tafel slope of 40.38 mV∙dec‍‍‍-‍1 in 1 M KOH, as well as outstanding durability in 80 h. This work provides a comprehensive design route for the high-efficient high entropy electrocatalyst for OER. [Display omitted] • The SO 4 2-modified (FeCoNiCrMn) 3 O 4 /HCS is prepared using microwave-solvothermal strategy. • The SO 4 2− drives morphology/structure evolution, intensifies surface reconstruction. • The HEO-S1/HCS exhibits a low overpotential of 237 mV at 10 mA cm−2 as well as excellent durability. [ABSTRACT FROM AUTHOR]

Maximum likelihood estimation (frequentist) and Bayesian estimation are two common parameter estimation methods. However, maximum likelihood estimation faces limitations, including the effect of outliers, computational complexity, and issues with ordinal categorical data, leading to biased estimates and inaccurate coverage probabilities. To address these limitations, this study employed a latent trait model with a Bayesian marginal likelihood of rank-based estimation for parameter estimation. The simulation results demonstrated favorable performance of the proposed method. Trace plots of all parameters showed good distribution and quick convergence, with the potential scale reduction factor not exceeding 1, indicating no convergence issues. Furthermore, the posterior predictive check showed the simulated data closely resembled the observed data, indicating the method effectively captures within-region variation through a latent trait parameter. Performance metrics like mean absolute error, root mean square error, and 95% confidence interval coverage probability revealed the estimates from the proposed Bayesian method surpassed those from classical approaches. In conclusion, a latent traits model with Bayesian marginal likelihood and rank-based estimation is considered a superior parameter estimation technique compared to classical methods, particularly for dealing with ordinal categorical data. [ABSTRACT FROM AUTHOR]

Abstract\nNOVELTY STATEMENTThe use of organic and inorganic amendments like stilbite-zeolite (SZ) and nano-biochar (NBC) in phytoremediation holds immense promise, long-term stability, and its effectiveness necessitate comprehensive research. This study aimed to evaluate their potential in mitigating heavy metal contamination in soil and plants. Our results shows that SZ and NBC treatments significantly impacted heavy metal levels, notably reducing arsenic (As), nickel (Ni), lead (Pb), cadmium (Cd), and mercury (Hg) accumulation in plant tissues. The treatments exhibited varying degrees of effectiveness in reducing heavy metal levels. Notably, SZ2 treatment decreased As and Pb levels by 33.33% and 20%, respectively, while NBC3 achieved even greater reductions, lowering As by 53.33% and Pb by 30%. Moreover, SZ2, SZ5, and NBC3 treatments halved Cd levels, showcasing their potential in mitigating heavy metal contamination in rice. However Hg levels remained largely unaffected, except for NBC1, which unexpectedly doubled its concentration. In soil, SZ2 treatment significantly reduced metal concentrations, particularly Cd (66.8% reduction) and Hg (70.7% reduction). Conversely, SZ3 and SZ7 treatments increased metal concentrations, suggesting that certain zeolite applications might enhance metal bioavailability. NBC treatments showed varying effectiveness, with NBC3 being the most effective, substantially reducing As, Pb, and Cd levels.The study uniquely evaluates the synergistic effects of SZ and NBC treatments on heavy metal reduction in rice grain. It identifies specific SZ and NBC treatments that significantly decrease arsenic, lead, and cadmium levels, with detailed analysis of both reductions and potential increases in metal bioavailability. This research provides critical insights into optimizing remediation strategies for enhanced soil health and food safety. [ABSTRACT FROM AUTHOR]

Understanding structure-property relationship in redox-active molecular species is of central importance in various fields, including many medicinal and chemical applications. The quest for performant organic electrodes in the context of energy storage calls for pioneering studies to develop new and possibly optimal materials. Beyond modifying the molecular design of the existing compounds through functionalization, expansion of the search enabling the advent of efficient new backbones can potentially lead to breakthroughs in this research area. The number of already identified families able to constitute negative organic electrodes is much lower than that of their positive counterparts, which calls for finding ways to bridge this gap. To expand the dataset of known predicted redox potentials and in view of reaching an educated guess about the abilities of some eventual new redox active electrodes, we examined the properties of pyrazine N,N'-dioxide (PZDO) and its fully methylated functionalized derivative (TeMePzDO). The aspects and mechanisms driving the various features characteristic of these compounds were unraveled through molecular and periodic DFT calculations combined with accurate electronic structure analysis. The predicted molecular redox/crystalline intercalation potentials lead to the classification of PZDO and TeMePzDO systems within the class of negative electrodes, with features that are significantly appealing compared to those of some existing systems with backbones suited for such kind of application. [ABSTRACT FROM AUTHOR]

Removal of Acid Red 88 (AR88) as an azo dye from the synthetic type of wastewater was studied in a laboratory-made constructed wetland microbial fuel cell (CW-MFC) inoculated with Shewanella oneidensis MR-1 (SOMR-1). Plant cultivation was implemented using a typical CW plant known as Cyperus alternifolius. The complexity of the SOMR-1 cell membrane having different carriers of electrons and H+ ions gives the microbe special enzymatic ability to participate in the AR88 oxidation link to the O2 reduction. Nernst equation developed based on analyzing the involved redox potential values in these electron exchanges is describable quantitatively in terms of the spontaneity of the catalyzed reaction. Power density (PD) at 100 mg/L of the AR88 under closed-circuit conditions in the presence of the plant was 11.83 mW/m2. Reduction of internal resistance positively affected the PD value. In determining degradation kinetics, two approaches were undertaken: chemically in terms of first- and second-order reactions and biochemically in terms of the mathematical equations for rate determination developed on the basis of substrate inhibitory concept. The first-order rate constant was 0.263 h−1 without plant cultivation and 0.324 h−1 with plant cultivation. The Haldane kinetic model revealed low ks and ki values indicating effective degradation of the AR88. Moreover, the importance of acclimatization in terms of the crucial role of lactate was discussed. These findings suggest that integrating the SOMR-1 electrochemical role with CW-MFC could be a promising approach for the efficient degradation of azo dyes in wastewater treatment. [ABSTRACT FROM AUTHOR]

Phosphate treatment at the Kpémé plant uses hydrocycloning with seawater, which produces phosphate sludge wastes discharged into the sea without any prior treatment. This waste is highly enriched in trace elements and is the source of water and coastal sediment pollution. The objective of this study is to highlight the pollutant load of the different phases of phosphate mud mining waste and their possible impact on the marine environment of the Togolese coast and certain neighboring countries, depending on their density. The methodology consists of a classification using a mini hydrocyclone Galaxi–Tower and a geochemical characterization of the phases of these sludgy mining wastes. A study of the bulk density of the phases obtained shows that the apatite-rich phase is denser than the clay-rich phase. Clay-rich phases will be transported over longer distances than apatite-rich phases, in accordance with the sea environment conditions prevailing on the coast. The clay-rich phase has a higher degree of acidity and redox potential than the apatite-rich phase. These phosphate sludgy wastes and the various phases are enriched in Cr, Cd, Cu, Co, Zn, Ni and Hg compared with the earth's crust. On the other hand, the light phase is more enriched in trace elements than the apatite-rich phase. The light phase has a higher apparent partition coefficient for all elements than the apatite-rich phase, except for Cd and Zn. In the dissolved solutions of clay-rich phases, Fe, Zn and Hg contents are higher than in apatite-rich phases. In contrast, Al, Cr, Cd, Cu and Ni contents are higher in apatite-rich phases than in clay-rich phases. Article Highlights: Separation of phosphate sludge waste phases according to density in seawater using a mini hydrocyclone Galaxi-Tower Assessment of trace element load of the particles constituting this sludgy phosphate waste and each separated phase Demonstration of trace element level in dissolved solution of phases during their possible transit in marine environment [ABSTRACT FROM AUTHOR]

Fully organic photocatalyst systems are highly attractive, not merely because they are transition‐metal free, but more importantly due to their unique and often potent reactivity. A detailed understanding of the various redox states, both ground and excited state, and specifically what structural parameters control them is therefore crucial for harnessing the full potential of these systems in organic synthesis. However, unlike their organometallic counterparts, detailed structure‐property relationships for organic photocatalysts are largely absent from the literature. In this study, we demonstrate linear free‐energy relationships across a range of key photophysical and electrochemical properties of 2,6‐diarylpyryliums. Electronic absorption and emission maxima can be carefully tuned over the ranges of 83 nm and 102 nm respectively. Intramolecular charge transfer (ICT) interactions were revealed in cases of substitution with polarizable heavy‐atoms. A strong linear dependence of ground state reduction potentials on substituent electronics was observed. Notably, the excited state reduction potential, E*red, could be controlled over a range of nearly 1000 mV. Systematic errors in computational modeling of ground and excited state redox potentials were identified and corrected. We believe the quantitative structure‐property relationships identified here provide foundational tools for rational and predictive organic photocatalyst design. [ABSTRACT FROM AUTHOR]

First examples of sterically crowded β‐ and meso‐arylated decaaryl triphyrin(2.1.1)s were synthesized by reacting β‐hexabromo meso‐tetraaryl triphyrin(2.1.1) with five different aryl boronic acids in THF/toluene/H2O (1 : 1 : 1) in the presence of catalytic amount of Pd(PPh3)4/Na2CO3 at 80 °C for 12–24 h. The X‐ray structure obtained for one of the decaaryl triphyrin(2.1.1)s revealed that the macrocycle exhibited saddle type of distortion due to steric crowding by bulky aryl substituents introduced at the six β‐carbons of meso‐tetraaryl triphyrin(2.1.1) unlike almost planar structure observed for β‐unsubstituted meso‐tetraaryl triphyrin(2.1.1). The absorption bands of decaaryl triphyrin(2.1.1)s were broadened and bathochromically shifted compared to meso‐tetraaryl triphyrin(2.1.1) and the redox potentials were dependent on the kind of aryl substituents present at the β‐pyrrole carbons in decaaryl triphyrin(2.1.1)s. DFT and TD‐DFT studies helped in understanding the alteration in the structure, spectral, and redox properties in decaaryl triphyrin(2.1.1)s compared to meso‐tetraaryl triphyrin(2.1.1). [ABSTRACT FROM AUTHOR]

High-performance potassium-ion batteries have received great attention for electrochemical energy storage owing to their low redox potential, abundant natural resources and excellent safety. As an advanced negative material, CoSe 2 has been widely investigated for potassium-ion batteries. Unfortunately, the pure CoSe 2 anode suffers from the fast capacity decay and sluggish kinetics, preventing its practical application. Herein, we introduce a novel strategy to fabricate the CoSe 2 nanoparticles embedded in one-dimensional mesoporous carbon nanofibers (denoted as 1D-CoSe 2 @CNFs) with superior high-rate property and good cycle stability for the first time. In this designed material, the conductive carbon nanofibers are loaded with CoSe 2 particles. The obtained 1D-CoSe 2 @CNFs anode shows a specific capacity of 706.3 mAh/g at 0.1 A/g and presents a high capacity retention ratio of around 96.3 % at 5 A/g over 400 cycles. Therefore, this fabricated 1D-CoSe 2 @CNFs nanocomposite can be employed as a novel negative electrode for potassium-ion storage. [ABSTRACT FROM AUTHOR]

This study introduces a computationally efficient urban building energy model (UBEM) to assess decarbonization strategies for the residential sector at the regional level. The model considers a range of inputs, including building characteristics, climate data, technology penetration, and occupant behavior. The model provides an economic analysis associating emission reduction potential with economic returns through an abatement cost curve, which is critical to designing cost-effective solutions. The model was validated at its full scale in Portugal, using actual consumption data from all municipalities. Key findings showed that lighting upgrades (100% LEDs) are the most cost-effective measure, offering the lowest abatement cost (−521 EUR/tonCO2eq) and a low discounted payback period of 2 years, while heat pumps for water heating provide the highest emission reduction potential, with an annual reduction of 863 tonnes of CO2eq annually, equivalent to a 20% reduction in national emissions. Additionally, behavioral measures achieved an annual reduction of 147 tonnes of CO2eq. The analysis further reveals that, while some measures might have a negative abatement cost at the national level, their economic viability varies locally, with certain municipalities incurring positive abatement costs, highlighting how local context affects the economic viability of decarbonization strategies. [ABSTRACT FROM AUTHOR]

Novel nuclear medicine therapeutics are being developed by labeling medium-molecular-weight compounds with short-lived alpha-emitting radionuclides. Fibroblast activation protein α (FAPα) is recognized as a highly useful molecular target, and its inhibitor, FAPI, is a compound capable of theranostics, both therapeutic and diagnostic, for cancer treatment. In this study, we compared the functions of two compounds that target FAPα: 211At-FAPI1 and 211At-FAPI2. First, in vitro screening procedures are generally accepted because of the low endogenous expression of FAPα. We suggest the usefulness of this 3D culture system for in vitro screening. Second, when FAPIs are used therapeutically, the expected therapeutic effects are often not achieved. Therefore, we compared the accumulation and excretion in tumor tissues and the anti-tumor effects based on the length of the linker in the compounds. The compounds were rapidly labeled using the Shirakami reaction. Doubling the linker length increased tumor retention. Additionally, the excretion pathway was altered, suggesting a potential reduction in toxicity. Although no significant differences were observed in the anti-tumor effects of 211At-FAPI1 and 211At-FAPI2, it was confirmed that the linker length affects the biological half-life. [ABSTRACT FROM AUTHOR]

Multicopper oxidases use Cu ions as cofactors to oxidize various substrates. High reduction potential at Type 1 Cu is considered as crucial for effective catalysis. Previous studies have shown that replacing the axial methionine ligand of the Type 1 Cu with leucine or phenylalanine leads to an increased reduction potential, but not always to higher enzyme activity. Here we present a study on six variants of the small laccase Ssl1 from Streptomyces sviceus, where the axial methionine ligand was substituted, and the effect of the axial ligand on reduction potential, activity, spectral properties and structure was investigated. Absorption, electronic circular dichroism and EPR spectra revealed the presence of a stronger coordinating axial ligand like oxygen, which influences the electronic and catalytic properties more than the nature of the amino acid side chain. The crystal structures of the Ssl1 variants were solved, which show that none of the amino acid side chains coordinate to the Cu. Instead, a water molecule is found in the axial coordination site, which support the spectroscopic data. Our findings highlight the importance of combining structural and spectroscopic methods to investigate the effect of amino acid exchange on multicopper oxidases. [ABSTRACT FROM AUTHOR]

Controlling the redox states of single‐walled carbon nanotubes (SWNTs) is important for the optimization of their real performances in various fields. By means of in situ photoluminescence (PL) spectroelectrochemical measurements, we report a successful modulation for the redox parameters (redox potentials and electrochemical band gap) of (6,5) and (7,5)SWNTs with a simple change in conjugated polymers (CPs) non‐covalently wrapped on the nanotubes. The large shift in the band gap (187 meV for (6,5)SWNTs and 101 meV for (7,5)SWNTs) was connected to the prominent difference in the interactions between the CPs and SWNTs as suggested by molecular dynamics (MD) simulations, while a striking difference in the π‐electrons states of CP/SWNTs enabled the tuning of SWNTs’ electronic states. Asymmetrical modulation for the reduction potential (LUMO) and oxidation potential (HOMO) of the SWNTs was observed as well. Our results can be promising for a simple but precise control of the electric states of SWNTs. [ABSTRACT FROM AUTHOR]

Zn metal anode is desired for aqueous batteries due to its high capacity and low redox potential. However, uneven Zn deposition and hydrogen evolution reaction (HER) have hindered the electrochemical reversibility and stability. Herein, an artificial solid electrolyte interphase (SEI) composed of metal center incorporated siloxane coupling with fluoride is in situ generated on Zn surface by a facile “etching–coating” process. This SZ‐SEI provides interaction sites with Zn2+, which helps with its desolvation at the interface and enlarges the transference number. Uniform Zn deposition underneath the layer is thus realized. Meanwhile, the SZ‐component hinders the adsorption of hydrogen atom and effectively suppresses HER. Thanks to the above effects, the cycle life of symmtric cells with SZ‐Zn electrodes extends to 2200 and 1400 h at the current densities of 10 and 20 mA cm−2, respectively. The coulombic efficiency of Zn plating/stripping also reaches 99.8% for 3800 cycles. In addition, the SZ‐Zn anode enables better rate capability and cycling stability of full cells. [ABSTRACT FROM AUTHOR]

The prejudice reduction potential of face-to-face intergroup contact is widely established, but we know much less about computer-mediated intergroup contact (online contact) specifically via social media where interactions are less controlled and mostly asynchronous. Additionally, much of the work on online contact has focused on positive, controlled contact, neglecting the effect of negative contact. We examined the effects of mediated contact via online posts with differing valence (positive, negative, and neutral) in three experimental studies, in an imaginary scenario (Study 1: N = 120) and a real intergroup scenario with South and North Indians (Study 2: N = 296, Study 3: N = 336). Main effects of One way and factorial ANOVA showed that contact valence significantly affected outgroup attitudes in Study 1 & 2 but was not replicated in Study 3, where quality and quantity of past contact and status differences emerged as significant predictors of attitudes. Multiple mediation analysis revealed that intergroup anxiety and quality of contact explained changes in attitudes, which was less affected by valence and more by regional identity and history of contact. Findings are discussed in light of the possibilities and limitations of asynchronous mediated contact on social media. [ABSTRACT FROM AUTHOR]

The synthesis of a novel large type double-layered cyclophanes has been successfully accomplished by free radical coupling reaction with the bis(N-alkylene benzothiazolium) dibromide salts as their important synthetic intermediates. The structures of the two-layered cyclophanes and the synthetic intermediates have been elucidated based on the NMR data and X-ray structural analysis, respectively. The two-layered cyclophanes consist of two different geometries, anti-two cyclic lactam amide rings inside and two bridges of disulfide bonds outside, which are unique and novel structures. Their physical properties were investigated by UV–Vis and redox potential, too. [ABSTRACT FROM AUTHOR]

Boron-β-diketonates are classical emissive materials that have been utilized in various fields, however, boron monothio-β-thioketonates, where one oxygen atom is exchanged for a sulphur atom, have not been explored in detail. To gain a better understanding of this class of materials, we synthesised various aryl substituted monothio-β-diketonate boron complexes with two different aryl substitutions on the boron center and studied their structural, optical and electrochemical properties. Single crystal X-ray analysis revealed that there is considerable deviation in B–O and B–S bond lengths for bis(pentafluorophenyl)boron complexes against diphenyl boron complexes. The bis(pentafluorophenyl)boron complexes have a relatively high absorption coefficient over diphenyl boron complexes. More importantly, a striking difference was observed for the emission behaviour of these compounds. The bis(pentafluorophenyl)boron complexes exhibit weak emission in the solution as well as in the solid state, whereas diphenyl boron complexes do not show any emission in either solution or the solid state. Further, the electrochemical study reveals that diphenyl boron complexes show a reduction potential that is more negative compared to the bis(pentafluorophenyl)boron complexes. The high absorption coefficient of the compounds pointed towards the possibility of high first order hyperpolarizability upon optical excitation, which motivated us to ascertain the nonlinear optical coefficients in the near infrared range, towards applicability of such compounds in optical limiting and switching. The open aperture Z-scan measurements at ultrashort time scales elucidated a few critical features of such compounds towards optical limiting applications. [ABSTRACT FROM AUTHOR]

In this paper, we are interested in the following nonlinear elliptic equation (0.1) { Δ u − V (x) u + u p = 0 in R N , u ∈ H 1 (R N) , where N ≥ 1 , p is subcritical, and V (x) is continuous, oscillates and decays to a positive constant at infinity. We use the localized energy technique and the Lyapunov–Schmidt reduction method to prove that the problem (0.1) has infinitely many positive solutions. Our result seems to be new for the existence of infinitely many positive solutions for elliptic equations with oscillatory potentials. [ABSTRACT FROM AUTHOR]

To improve alkaline water electrolysis, catalyst coated diaphragms are prepared on Zirfon UTP 500 using polyvinylalcohol as a binder and Raney Ni and Pt (20% Pt/C; nanoparticular Pt) as catalysts to enhance the hydrogen evolution reaction. The catalyst coated diaphragms are tested under close to industrial conditions to assess their electrochemical performance and stability (60+ h). Raney Ni loaded diaphragms show 200 mV cell potential reduction at low temperature, and 150 mV at high temperature throughout the entire current density range. Nanoparticulate Pt and Pt/C loaded diaphragms perform well at low current densities (<30 mA/cm2), where a overpotential reduction of 150 mV is attained. At higher current densities (>30 mA/cm2) the reduction is smaller at only 50–100 mV throughout the entire temperature range, caused by an increase in Tafel slope. Long-term measurements and SEM/EDX show that the catalyst layers become unstable after several hours of experiments. [Display omitted] • Pt and Raney Ni coated diaphragms with PVA tested were under industrial conditions. • Flow cell measurements showed cell potential improvement of 100–150 mV. • Tafel slope for Pt in 27 wt% KOH small at low currents and large at high currents. • Raney Ni performed excellent throughout all temperature and current ranges. • Stability tests of up to 60 h were conducted. [ABSTRACT FROM AUTHOR]

Microbial electrosynthesis (MES) is an innovative technology that employs microbes to synthesize chemicals by reducing CO 2.This study explores the CH 4 production performance at different cathodic reduction potentials in MES. In this study, in situ H 2 production on the surface of composite electrode was realized by regulating cathode potential. Pathway for H 2 -mediated CH 4 synthesis was the main synthesis pathway, but it was susceptible to interfere from the external environment (such as cathode potential, pH). The optimal CH 4 production potential was −1.0 V vs Ag/AgCl, meanwhile the CH 4 synthesis rate was 58 ± 0.4 mLm−2d−1 and the CE was 67 ± 0.5%. Excessively high reduction potentials (−1.4 V vs Ag/AgCl) reduce the activity of microbial populations at the cathode. Synergistic interactions between H 2 -producing bacteria (Hydrogenophaga , Clostridium , Enterobacter , and Escherichia coli) and Hydrogenotrophic methanogens (Methanobacterium and Methanomassiliicocus) promoted efficient synthesis of CH 4. These insights provide new perspectives on reactor operation, thus contributing to the efficiency of MES. There could be three pathways for the synthesis of CH 4 , including directly synthesize CH 4 by Methanosarcinia, H 2 -mediated CH 4 synthesis and acetate-mediated CH 4 synthesis. The main pathways is that H 2 -mediated CH 4 synthesis. [Display omitted] • At −1.0V vs Ag/AgCl, CH 4 yield was the highest, 58 ± 0.4 mL m−2d−1. • In situ synthetic H 2 facilitated the H 2 -mediated CH 4 synthesis. • The synergy of H 2 -producing bacteria and hydrogenotrophic methanogens. • The principal methanogenic pathway is hydrogenotrophic methanogenesis. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting for hydrogen evolution is a highly topical subject in academic research and a promising approach for sustainable fuel production from solar energy. Due to the mismatched energy diagram of the photosensitizer (especially semiconductor‐based materials where band‐edge engineering is not trivial) and the redox potential of the half‐reactions of water splitting, photocatalytic H2 generation from water splitting is usually accelerated by the addition of hole scavengers, i.e. sacrificial reagents such as alcohols, amines, and thiols. However, the source of the protons of the evolved H2 is often neglected, and it is questionable whether such systems are really water splitting. Here, we discuss recent reports on sacrificial reagent‐assisted photocatalytic water splitting and present our recent findings, which showcase that the sacrificial reagent in the investigated photocatalytic water splitting systems inherently undergoes acceptorless dehydrogenation, with H2O serving as the proton shuttle, the amount of which doesn't change during the course of the reaction. [ABSTRACT FROM AUTHOR]

Paddy fields are important anthropogenic emission sources of methane (CH4). However, it is not clear how rice root development and rhizosphere soil properties affect CH4 emissions. Therefore, we selected rice varieties with similar growth periods but different root traits in the local area. We measured CH4 emission fluxes, cumulative CH4 emissions, root dry weight, root length, and the dissolved organic carbon (DOC), microbial biomass carbon (MBC), redox potential (Eh), ammonium nitrogen ( N H 4 + –N), and nitrate nitrogen ( N O 3 − –N) contents in rhizosphere soil. Methanogens and methanotrophs are crucial factors influencing CH4 emissions; thus, their abundance and community composition were also assessed. The result showed that CH4 fluxes of each rice variety reached the peak at tillering stage and jointing-booting stage. The CH4 emissions in tillering stage were the largest in each growth period. CH4 emissions had negative correlations with root length, root dry weight, Eh N O 3 − –N, methanotroph abundance, and the pmoA/mcrA ratio, and positive correlations with N H 4 + –N, MBC, DOC, and methanogen abundance. Path analysis confirmed methanogens and methanotrophs as direct influences on CH4 emissions. Root development and rhizosphere soil properties affect CH4 emissions indirectly through these microbes. This study suggests that choosing rice varieties with good root systems and managing the rhizosphere soil can effectively reduce CH4 emissions. [ABSTRACT FROM AUTHOR]

The redox properties of half-sandwich rhodium complexes supported by 2,2′-bipyridyl (bpy) ligands can be readily tuned by selection of an appropriately substituted derivative of bpy, but the influences of single substituents on the properties of such complexes are not well documented, as disubstituted bpy variants are much more common. Here, the synthesis, characterization, and redox properties of two new [Cp*Rh] complexes (where Cp* is η5-1,2,3,4,5-pentamethylcyclopentadienyl) supported by the uncommon mono-substituted ligands 4-chloro-2,2′-bipyridyl (mcbpy) and 4-nitro-2,2′-bipyridyl (mnbpy) are reported. Single-crystal X-ray diffraction studies and related spectroscopic experiments confirm installation of the single substituents (–Cl and –NO2, respectively) on the bipyridyl ligands; the precursor monosubstituted ligands were prepared via a divergent route from unsubstituted bpy. Electrochemical studies reveal that each of the complexes undergoes an initial net two-electron reduction at potentials more positive than that associated with the parent unsubstituted complex of bpy, and that the complex supported by mnbpy can undergo a third, chemically reversible reduction at −1.62 V vs. ferrocenium/ferrocene. This redox behavior is consistent with inductive influences from the substituent groups on the supporting ligands, although the nitro group uniquely enables addition of a third electron. Spectrochemical studies carried out with UV-visible detection confirm the redox stoichiometry accessible to these platforms, highlighting the rich redox chemistry and tunable behavior of [Cp*Rh] complexes supported by bpy-type ligands. [ABSTRACT FROM AUTHOR]

Rechargeable magnesium batteries (RMBs) have the potential to provide a sustainable and long‐term solution for large‐scale energy storage due to high theoretical capacity of magnesium (Mg) metal as an anode, its competitive redox potential (Mg/Mg2+:−2.37 V vs. SHE) and high natural abundance. To develop viable magnesium batteries with high energy density, the electrolytes must meet a range of requirements: high ionic conductivity, wide electrochemical potential window, chemical compatibility with electrode materials and other battery components, favourable electrode‐electrolyte interfacial properties and cost‐effective synthesis. In recent years, significant progress in electrolyte development has been made. Herein, a comprehensive overview of these advancements is presented. Beginning with the early developments, we particularly focus on the chemical aspects of the electrolytes and their correlations with electrochemical properties. We also highlight the design of new anions for practical electrolytes, the use of electrolyte additives to optimize anode‐electrolyte interfaces and the progress in polymer electrolytes. [ABSTRACT FROM AUTHOR]

It is still a great challenge to achieve high selectivity of ethanol in CO2 electroreduction reactions (CO2RR) because of the similar reduction potentials and lower energy barrier of possible other C2+ products. Here, we report a MOF‐based supported low‐nuclearity cluster catalysts (LNCCs), synthesized by electrochemical reduction of three‐dimensional (3D) microporous Cu‐based MOF, that achieves a single‐product Faradaic efficiency (FE) of 82.5 % at −1.0 V (versus the reversible hydrogen electrode) corresponding to the effective current density is 8.66 mA cm−2. By investigating the relationship between the species of reduction products and the types of catalytic sites, it is confirmed that the multi‐site synergism of Cu LNCCs can increase the C−C coupling effect, and thus achieve high FE of CO2–to–ethanol. In addition, density functional theory (DFT) calculation and operando attenuated total reflectance surface‐enhanced infrared absorption spectroscopy further confirmed the reaction path and mechanism of CO2–to–EtOH. [ABSTRACT FROM AUTHOR]

We report here a photoinduced iron-catalyzed fluoroalkylation-peroxidation of activated and/or unactivated alkenes with fluoroalkyl carboxylic acids and hydroperoxide. The ligand-to-iron charge transfer strategy effectively overcomes the high redox potential of the fluoroalkyl carboxylic acids, facilitating the difunctionalization reaction to occur smoothly under mild reaction conditions. The late-stage functionalization of drug and natural product derivatives was also demonstrated. [ABSTRACT FROM AUTHOR]

Intracellular calcium dynamics is key to regulating various physiological events. Myotube formation by myoblast fusion is controlled by the release of Ca2+ from the endoplasmic reticulum (ER), and the calpain (CAPN) family is postulated to be an executioner of the process. However, the activation of a specific member of the family or its physiological substrates is unclear. In this study, we explore the involvement of a CAPN in myoblast differentiation. Time-course experiments showed that the reduction in potential substrates of calpains, c-Myc and STAT3 (signal transducer and activator of transcription 3) and generation of STAT3 fragments occurred multiple times at an early stage of myoblast differentiation. Inhibition of the ER Ca2+ release suppressed these phenomena, suggesting that the reduction was dependent on the cleavage by a CAPN. CAPN5 knockdown suppressed the reduction. In vitro reconstitution assay showed Ca2+- and CAPN5-dependent degradation of c-Myc and STAT3. These results suggest the activation of CAPN5 in differentiating myoblasts. Fusion of the Capn5 knockdown myoblast efficiently occurred; however, the upregulation of muscle-specific proteins (myosin and actinin) was suppressed. Myofibrils were poorly formed in the fused cells with a bulge where nuclei formed a cluster, suggesting that the myonuclear positioning was abnormal. STAT3 was hyperactivated in those fused cells, possibly inhibiting the upregulation of muscle-specific proteins necessary for the maturation of myotubes. These results suggest that the CAPN5 activity is essential in myoblast differentiation. [ABSTRACT FROM AUTHOR]

The restinga habitats are coastal psammophilous environments, with only 0.47% of the original area remaining in Brazil. This environment embraces at least 36 known species of lizards, 7 of them being endemic. Besides direct anthropogenic impacts, climate change raises new cautions on Brazilian restingas‐endemic lizards conservation. We evaluated the current and future potential distribution of the endemic lizards from Brazilian restingas, considering different climate change scenarios. We hypothesized shifts in the potential distribution of the restinga‐endemic lizards. We conducted ecological niche modeling to predict the potential distribution of Brazilian restingas‐endemic lizards. Here, we used an ensemble of three modeling algorithms (Bioclim, GLM, and SVM). In predicting the effects of climate change on their future distributions, we used intermediate and pessimistic socio‐economic pathway scenarios (SSP3 70 and SSP5 85, respectively) considering projections for 2081–2100. Furthermore, we calculate the extent of future potential distribution covered by the current spatial configuration of integral protection areas to assess if they will still be effective in conserving the species in the future. We did this by binarizing predicted potential distribution with a threshold of 0.8. Our data pointed out that the species will have their potential distribution area altered for 2081–2100, considering climate change scenarios. Tropidurus hygomi, Glaucomastix abaetensis, and G. itabaianensis overlapped along their predicted potential distribution for the present and future. The same was found to Ameivula nativo and Liolaemus lutzae. Moreover, our results showed a potential marked reduction of potential distribution covered PAs. The recognition of potential distribution areas discussed here enables focal and urgent conservation strategies, besides bringing up alerts on protected areas' role in conserving these species under climate change scenarios. We propose creating planning policies using space and time criteria and developing long‐term studies, besides promoting educational programs aiming at environmental conservation. Thus, we expect our research to contribute to the protection of the land over Brazilian restingas‐endemic lizards' distribution. [ABSTRACT FROM AUTHOR]

Background: Macrobrachium amazonicum is an opportunistic and omnivorous species that primarily feeds on plant material. Recent studies have shown that Endo-β-1,4-glucanase and Endo-β-1,4-mannanase are expressed in the transcriptome of adult specimens, while juveniles are capable of digesting nutrients from purified cellulose in their diet. In organisms that degrade raw plant material, laccase plays a key role in oxidizing phenolic compounds found in lignin, leading to its depolymerization and increasing access to cellulose and hemicellulose microfibrils. Objective: In this study, we conducted an in silico identification and characterization of the laccase-encoding gene, as this enzyme is linked to lignin biodegradation in herbivorous crustaceans. Methods: We analyzed the transcriptomes of the hepatopancreas from adult M. amazonicum, sequenced using the Illumina HiSeq 2500 platform. Subsequently, bioinformatics analyses were conducted to predict the conserved regions and active sites associated with laccase activity. Results: A complete open reading frame (ORF) of the laccase protein was identified in all datasets, comprising 609 amino acids. The top 40 similarity hits corresponded exclusively to crustaceans such as prawns, crayfish, and crabs (86.3–51.4%), while the highest divergence was observed in relation to fungi, plants, and bacteria. Three conserved domains were detected, along with the complete set of copper-binding centers (T1Cu, T2Cu, and T3Cu). A notable variable residue was methionine, suggesting a reduced redox potential in M. amazonicum laccase. Conclusion: These findings, combined with recent reports on the nutritional requirements of M. amazonicum, contribute to a deeper understanding of the digestive physiology of this species and offer valuable insights into its ability to utilize plant fibers as energy sources. [ABSTRACT FROM AUTHOR]