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Digital advancements have reshaped the sales channels for industrial products like chemical fertilizers, allowing for the elimination of certain intermediaries. Utilizing survey data from 1374 rice‐growing smallholder farmers across counties in central China, this study explored the impact of disintermediation in chemical fertilizer sales channels on application rates among smallholder farmers. Benchmark regression analyses indicated that channel disintermediation significantly decreased chemical fertilizer application across various scenarios. Additionally, the alignment of contractual factors and technical services between chemical suppliers and farmers, facilitated by disintermediation, reduced chemical fertilizer application. Heterogeneity analysis revealed that the reduction in chemical fertilizer application due to channel disintermediation was more pronounced among farmers with higher digital literacy or lower production capacity. These findings highlighted the importance of encouraging chemical suppliers with direct‐to‐consumer channels to enhance their technical services and increase supervision over the quality of their products and services, thereby building trust among farmers and facilitating their adaptation to changes in the sales channel structure. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The reaction between tripodal trisamidophosphine ligand H3PN3Ar and V(Mes)3(THF) (Mes = mesityl) yields the vanadium(III) complex (PN3Ar)V (1) with an open site in the axial position, which could coordinate with THF, pyridine, and NH3 to form the corresponding adducts (2—4). The vanadium(III) center is redox‐active, as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction. Notably, a novel dinitrogen divanadium complex with a bridging N2 ligand, {K(THF)}2{[PN3Ar]V}2(μ‐N2) (6), was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N2 atmosphere. The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations. Additionally, these vanadium complexes (1, 5, 6) can serve as catalysts for the conversion of N2 into N(SiMe3)3 in the presence of reductants and Me3SiCl. [ABSTRACT FROM AUTHOR]

This work reports a practical approach for C−O and C−C bond formation reactions catalysed by Pd nanoparticles supported on Luffa sponge (PdNPs@LS).PdNPs@LS were prepared via a green route in‐situ by using ethanol as solvent, and lignin content present in the luffa sponge could work as an effective reducing reagent to reduce Pd(II) to Pd(0) without any harsh chemical used for reduction. The bio‐based support used i. e. Luffa sponge extracted from the waste feedstock of Luffa guard in a simple filtration method is a cheap, biodegradable, abundant and renewable source with netting‐like three‐dimensional porous structure. Without significant loss of its activity the PdNPs@LS could be easily recovered and recycled for at least three times. The catalyst is characterized by FT‐IR, TGA, SEM‐EDX, TEM, and XPS analyses. [ABSTRACT FROM AUTHOR]

A one‐pot, ecologically friendly method for the preparation of Fe/Ni, Fe/Co and Co/Ni bimetallic magnetic nanoparticles (MNPs) was reported, using glycerol as both a solvent and reducing agent. Six different bimetallic MNPs by varying the proportions of transition metals, namely, Fe, Co and Ni were synthesized by the chemical reduction method. The catalytic efficiency of the synthesized nanoparticles (NPs) was explored for the reduction of 4‐nitrophenol, and the reaction rate for different catalysts was systematically analysed. Especially, glycerol‐Fe/Co (1:3) bimetallic nanoparticles as a magnetically recoverable catalyst had higher catalytic activity than the other bimetallic nanoparticles for the reduction of 4‐nitrophenol to 4‐aminophenol in the presence of sodium borohydride. The reduction process was monitored by UV–visible spectroscopy, and the reaction was complete within 8 min. The kinetic study shows 99% conversion of 4‐nitrophenol to 4‐aminophenol, and the rate constant is 0.593 min−1. Furthermore, the glycerol‐Fe/Co (1:3) MNPs were retrieved from the reaction mixture and subsequently utilized in five consecutive cycles, demonstrating both the reusability and durability of the NPs as a catalyst. This research was remarkable for its fast reaction kinetics, simplified one‐pot conversion of 4‐nitrophenol to 4‐aminophenol without the need for mechanical or magnetic stirring and in‐depth study of six bimetallic MNPs' catalytic properties in nitro reduction. These findings explored the potential benefits of bimetallic magnetic NPs for the synthesis of 4‐aminophenol products. [ABSTRACT FROM AUTHOR]

In this study, the synthesis, followed by a detailed evaluation of the structural, optical, and electrical properties of the N‐ZnO/N‐rGO nanocomposite prepared using a one‐step low‐temperature hydrothermal process, is reported. By employing N, N‐dimethylformamide (DMF) as the reducing agent and urea as the nitrogen precursor, simultaneous reduction and nitrogen doping are achieved in the nanocomposite. X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and Raman measurements are used for the structural evaluation. The formation of composites is verified using the ZnC/ZnOC bonds in the XPS. The nitrogen doping in the nanocomposites varies from 0.8% to 1.8%. The major nitrogen moieties observed here include pyrrolic N, pyridinic N, and graphitic N. The electrical response is measured using current–voltage characteristics, and enhanced conductivity was observed in the sample with the highest percentage of pyrrolic N. This is attributed to the superior electron transport mechanism of pyrrolic N in the graphene structure. The current response is found to increase from 2 to 10 μA from ZnO/rGO to N‐ZnO/N‐rGO nanocomposite. The integration of N‐rGO support with extensively doped pyrrolic end groups for the N‐ZnO nanoparticles has been found to improve the conduction mechanism and is hence promising for many applications. [ABSTRACT FROM AUTHOR]

Among hydrogen production methods, water electrolysis stands out, but its efficiency is hampered by the substantial energy barrier of the oxygen evolution reaction (OER). To address this, incorporating electron‐deficient boron (B) into Co–Fe hydroxide (CoFeOxHy) promotes higher oxidation states of involved metals, greatly enhancing OER activity and charge transfer capabilities. Herein, the synthesis of a range of amorphous CoFeB nanoparticles with varying Fe to (Co+Fe) atomic ratios achieved through a simple chemical reduction method using CoFe‐Prussian blue analogs as precursors and employing Mössbauer spectroscopy to observe structural characteristics before and after transformation is reported. Among these nanoparticles, the CoFe0.25B variant, exhibiting favorable electrochemical properties, is chosen and subsequently subjected to hydrolysis to yield CoFe0.25BOH nanoparticles, serving as an active catalyst for OER. At a current density of 10 mA cm−2, the overpotentials for CoFe0.25OxHy and CoFe0.25BOH are 362 and 310 mV, respectively, with Tafel slopes decreasing from 393 to 93 mV dec−1. Furthermore, the i–t test reveals no significant loss of electrochemical performance within 24 h, substantiating the efficacy of enhancing the electrocatalytic performance of CoFeOxHy through the introduction of electron‐deficient elements. This research offers novel insights into the development of efficient and stable water electrolysis catalysts. [ABSTRACT FROM AUTHOR]

Phosphaphenalenes, extended π conjugates with the incorporation of phosphorus, are attractive avenues towards molecular materials for the applications in organic electronics, but their electron accepting ability have not been investigated. Herein we present systematic studies on the reductive behavior of a representative phosphaphenalene and its oxide by chemical and electrochemical methods. The chemical reduction of the phosphaphenalene by alkali metals reveals the facile P−C bond cleavage to form phosphaphenalenide anion, which functions as a transfer block for structure modification on the phosphorus atom. In contrast, the pentavalent P‐oxide reacts with one or two equivalents of elemental sodium to form stable radical anion and dianion salts, respectively. [ABSTRACT FROM AUTHOR]

Carbon materials are of great significance in state‐of‐the‐art electrochemical CO2 reduction (ECR) as key components such as electrocatalysts, gas diffusion electrodes, and current collectors. Notably, dimensionalities of carbons and related manipulations play vital roles in boosting ECR performance, e.g., mass/charge transfer dynamics, exposure of active sites, reaction space, product's Faradaic efficiency/selectivity, and durability. Here, recent endeavors in dimensionality engineering toward advanced carbon‐based materials for ECR is first summarized, including pure carbons (e.g., carbon nanotube and graphene) and carbon composites, and highlight the dimensionality‐dependent properties toward ECR performance. Various engineering strategies referring to dimensionality modulation and integration have been summarized, e.g., top‐down, bottom‐up, and soft chemical approaches. Design principles of dimensionality‐varied carbons are elaborated, the impacts of dimensionalities of carbons and related surface chemistry (e.g., functional group, wettability, and electronic structure) on ECR kinetics and product‐targeted mechanisms are also scrutinized. Some insights into how the dimensionality manipulation of carbons elevates performance of carbon‐based materials in mass/charge transfer acceleration, ECR kinetics, and product selectivity are provided. At last, a perspective for challenges and future development of dimensionality‐varied carbon materials is discussed. This review aims at providing guidance for customizable construction of carbon materials with dimensionality dependence toward green and energy‐saving electrosynthesis systems. [ABSTRACT FROM AUTHOR]

The chemical reduction within a family of organic selenocyanates, as masked selenols, using reducing agents, such as Rongalite, sodium dithionite, and sodium thiosulfate is investigated. Using Rongalite, the corresponding diselenides were obtained quantitatively and selectively in very good to excellent yields (51–100 %) starting from alkyl, aryl, and benzyl selenocyanates. The scope of the reaction is unaffected by the electronic nature of the substituents. Furthermore, the reducing agent, Rongalite, is compatible with hydrolysable and reducing‐sensitive functional groups. Additionally, a simple methodology employing the in‐situ generated benzyl selenolate anion (PhCH2Se−) to promote aliphatic nucleophilic substitution, epoxide ring opening, and Michael addition reactions has been developed; thus, extending the structural diversity of the synthesized selenium derivatives. [ABSTRACT FROM AUTHOR]

Hydrogen production by direct seawater electrolysis is an alternative technology to conventional freshwater electrolysis, mainly owing to the vast abundance of seawater reserves on earth. However, the lack of robust, active, and selective electrocatalysts that can withstand the harsh and corrosive saline conditions of seawater greatly hinders its industrial viability. Herein, a series of amorphous transition‐metal phospho‐borides, namely Co‐P‐B, Ni‐P‐B, and Fe‐P‐B are prepared by simple chemical reduction method and screened for overall alkaline seawater electrolysis. Co‐P‐B is found to be the best of the lot, requiring low overpotentials of ≈270 mV for hydrogen evolution reaction (HER), ≈410 mV for oxygen evolution reaction (OER), and an overall voltage of 2.50 V to reach a current density of 2 A cm−2 in highly alkaline natural seawater. Furthermore, the optimized electrocatalyst shows formidable stability after 10,000 cycles and 30 h of chronoamperometric measurements in alkaline natural seawater without any chlorine evolution, even at higher current densities. A detailed understanding of not only HER and OER but also chlorine evolution reaction (ClER) on the Co‐P‐B surface is obtained by computational analysis, which also sheds light on the selectivity and stability of the catalyst at high current densities. [ABSTRACT FROM AUTHOR]

Carbon dioxide is a greenhouse gas that contributes to global warming but fortunately can be removed via chemical conversion processes that often involve a reduction step. Dielectric barrier discharge (DBD) plasma is an effective way to promote chemical reduction processes but requires a catalyst for energetically demanding reactions. In this study, the rapid conversion of CO2 into solid carbon via a DBD plasma is reported using dispersed liquid metal Ga which is first converted into GaOOH particles to ultimately form a GaOOH/C nanocomposite. Raman and X‐ray diffraction (XRD) experiments indicate that amorphous activated carbon is formed after the plasma treatment. Further analysis demonstrates that highly dispersed sub‐nano‐sized carbon particles containing oxygen functional groups are formed uniformly on the GaOOH surface. The CO2 conversion mechanism suggests that plasma electrons activate CO2 molecules, while plasma‐generated oxygen vacancies on the catalyst surface help dissociate CO2 into solid carbon. This work opens a new approach for synthesizing materials comprising of highly dispersed sub‐nano‐sized carbon on a metal oxide support suitable for other applications such as adsorption, heterogenous catalysis, and energy conversion. [ABSTRACT FROM AUTHOR]

A life cycle assessment (LCA) study was completed to understand the environmental impacts associated with the land application of wastes produced from rural food‐processing operations for final disposal. The system boundaries for the two comprised scenarios included the storage of the produced non‐agriculture source material (NASM), transportation to an applicable location, land application of the NASM, and the impacts of the final emissions to the soil and groundwater for a full year. The Tool for the Reduction and Assessment of Chemicals and Other Environmental Impacts (TRACI) v2.1 was selected as the impact assessment method. Furthermore, SimaPro 8.0.4.26 was the LCA model version that was used with all the databases included. Overall, the LCA study showed that the most significant environmental impacts associated with the disposal process resulted from carcinogenic and eutrophication emissions. The component that contributed the most to carcinogenic impacts was found to be from the material required to create the concrete storage tank. Additionally, eutrophication was identified to be a potential significant impact, if proper setback requirements are not followed for the NASM material. Results of the study look to inform stakeholders about the benefits and risks encountered from NASM disposal. Practitioner Points: Life cycle assessment was completed on a representative NASM disposal system using land application.Concrete tank used for storage of NASM had the most significant impact in carcinogenic emissions.Eutrophication impacts were the second most significant impact behind carcinogenic emissions. [ABSTRACT FROM AUTHOR]

In the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron‐hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high‐performance photocathode for multi‐electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high‐throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly‐functionalized covalent networks for boosting eight‐electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo‐accumulating assembly and multi‐electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems. [ABSTRACT FROM AUTHOR]

We disclose an indenoannulated tridecacyclene comprising a central cyclooctatetraene moiety with multiple adjacent pentagonal rings which is accessible in a concise synthetic sequence. The saddle‐shaped geometry of the non‐benzenoid polycyclic scaffold and its unique packing behavior in the solid state were characterized by X‐ray crystallography. In electrochemical studies, the compound undergoes seven reversible redox events comprising five reductions and two oxidations. The dicationic and dianionic species obtained by chemical oxidation and reduction, respectively, were characterized spectroscopically in solution. Density functional theory calculations were applied to provide insights into aromaticity evolution in the respective charged species, highlighting the beneficial effect of the non‐benzenoid moieties on charge stabilization [ABSTRACT FROM AUTHOR]

Oxygen vacancies are one of the prominent types of defects in metal oxides. In addition to their role in modifying the electronic properties in solids, these sites have been shown to activate chemical bonds. As a result, the use of defect‐rich metal oxides in the organic transformations is promising. The article gives an overview of various chemical processes that are in use for the chemical reduction of aromatic nitro compounds to amines. Recently, application of oxygen vacancies in transition metal oxide for the selective reduction of aromatic nitro compounds to the corresponding amines has emerged as a new method of synthesis of amines. Oxygen vacancies in reducible oxide such as CuO have been shown to decompose hydrazine hydrate to H2 and in situ cause the reduction of nitro arenes to corresponding amines. This concept article discusses the literature pertaining to the synthesis of nitro reduction reaction, various strategies employed thus far and the place the defect‐mediated synthesis holds. The article also discusses the perspectives and challenges that remain to be addressed to gain more insights into the mechanistic understanding of the role of oxygen vacancies in nitro reduction and beyond. [ABSTRACT FROM AUTHOR]

Benchtop NMR provides improved accessibility in terms of cost, space, and technical expertise. In turn, this encourages new users into the field of NMR spectroscopy. Unfortunately, many interesting samples in education and research, from beer to whole blood, contain significant amounts of water that require suppression in 1H NMR in order to recover sample information. However, due to the significant reduction in chemical shift dispersion in benchtop NMR systems, the sample signals are much closer to the water resonance compared to those in a corresponding high‐field NMR spectrum. Therefore, simply translating solvent suppression experiments intended for high‐field NMR instruments to benchtop NMR systems without careful consideration can be problematic. In this study, the effectiveness of several popular water suppression schemes was evaluated for benchtop NMR applications. Emphasis is placed on pulse sequences with no, or few, adjustable parameters making them easy to implement. These fall into two main categories: (1) those based on Pre‐SAT including Pre‐SAT, PURGE, NOESY‐PR, and g‐NOESY‐PR and (2) those based on binomial inversion including JRS and W5‐WATERGATE. Among these schemes, solvent suppression sequences based on Pre‐SAT offer a general approach for easy solvent suppression for samples with higher analyte concentrations (sucrose standard and Redbull™). However, for human urine, binomial‐like sequences were required. In summary, it is demonstrated that highly efficient water suppression approaches can be implemented on benchtop NMR systems in a simple manner, despite the limited spectral dispersion, further illustrating the potential for widespread implementation of these approaches in education and research. [ABSTRACT FROM AUTHOR]

Optimally increasing the catalytic activity of Co3O4‐based materials is crucial for promoting their practical applications for acetone detection; however, this still remains challenging. Herein, a strategy is proposed in this work to increase the catalytic activity of Co3O4 toward the oxidation of acetone through the synergistic effect of boron doping and chemical reduction, which can substantially improve the sensing performance for acetone detection. The characterization results confirm that the present strategy facilitates the formation of more oxygen vacancies and increases the content of Co2+ ions serving as active sites. As expected, the optimal sensor yields a higher response. To extend the practical application to the auxiliary diagnosis of diabetes through exhaled breath, the optimal sensors distinguished between acetone concentrations in the breath of healthy individuals and in the simulated breath of patients with diabetes. Detailed gas‐sensing measurements reveal that the enhanced acetone sensing performance is attributed to the increased catalytic activity of materials for oxidation of acetone by the Mars–van Krevelen, Langmuir–Hinshelwood, and Eley–Rideal mechanisms. This study provides new insights into the fabrication of high‐performance metal oxide‐based gas sensors by improving the catalytic activity of sensing materials. [ABSTRACT FROM AUTHOR]

Chemical reduction of a [4]cumulene with cesium metal was explored, and the structural changes stemming from electron acquisition are detailed using X‐ray crystallography. It is found that the [4]cumulene undergoes dramatic geometric changes upon stepwise reduction, including bending of the cumulenic core and twisting of the endgroups from orthogonal to planar. The structural deformation is consistent with early theoretical reports that suggest that the twisting should occur upon reduction of both even and odd [n]cumulenes. The current results, on the other hand, are inconsistent with a previous experimental study of a [3]cumulene in which the predicted twisting is not observed upon reduction. DFT calculations reveal that the barrier to deformation is an order of magnitude lower in a [3]cumulene than a [4]cumulene, allowing the barrier to be overcome in the solid‐state. [ABSTRACT FROM AUTHOR]

Cellular DNA and RNA are decorated with diverse chemical modifications, which add new layers to gene regulation and play crucial roles across development and disease progression. Interest in understanding the functions of DNA and RNA modifications, as well as the related molecular mechanisms, has been growing, driving progress in developing chemical and biochemical tools to detect specific modifications. New technologies are important not only for uncovering biological functions, but also for driving conceptual revolutions. In this review, we highlighted our recent advances in developing new chemical tools to detect DNA and RNA modifications in a direct, quantitative, and base‐resolution manner. These includes a novel borane reduction chemistry for DNA methylation sequencing; new cytosine modificaiton oxdation chemistry for enhanced DNA hydroxymethylation sequencing; and a novel bromoacrylamide cyclization chemistry for RNA pseudouridylation sequencing. We present a mechanistic overview of these tools and their applications in epigenetic and epitranscriptomic research. [ABSTRACT FROM AUTHOR]

Molybdenum‐ or tungsten‐dependent formate dehydrogenases have emerged as significant catalysts for the chemical reduction of CO2 to formate, with biotechnological applications envisaged in climate‐change mitigation. The role of Met405 in the active site of Desulfovibrio vulgaris formate dehydrogenase AB (DvFdhAB) has remained elusive. However, its proximity to the metal site and the conformational change that it undergoes between the resting and active forms suggests a functional role. In this work, the M405S variant was engineered, which allowed the active‐site geometry in the absence of methionine Sδ interactions with the metal site to be revealed and the role of Met405 in catalysis to be probed. This variant displayed reduced activity in both formate oxidation and CO2 reduction, together with an increased sensitivity to oxygen inactivation. [ABSTRACT FROM AUTHOR]

Glycerol (GL) represents a widespread agro‐industrial waste. Its valorization is pivotal for a sustainable society because GL is a renewable compound deriving from biomass, but it has a high oxygen to carbon ratio, compared with feedstock used in the energy and chemistry sectors. Oxygen‐poor derivatives are easily and immediately transferable to the industry, avoiding a deep and pressing modification of the plants. From this perspective, keeping the carbon content but with an oxygen content reduction, we could effectively obtain the enhancement of the recovery and the use of GL converting it into attractive industrial building‐blocks. In this Review, we present and discuss the up‐to‐date results about the chemical reduction of GL into products with 3 carbon and 0, 1, or 2 oxygen atoms. The focus is on the transition metal (TM) catalysts that have made the hydrogenation reactions of GL possible, partitioning the metals into early and late, based on their position in the periodic table. This discussion will contribute to select and develop new catalysts aimed at the improvement of the yield and of the selectivity in the hydrogenation reactions of GL. [ABSTRACT FROM AUTHOR]

Exploration of the reduction chemistry of the 2,2'‐bipyridine (bipy) lanthanide metallocene complexes Cp*2LnCl(bipy) and Cp*2Ln(bipy) (Cp* = C5Me5) resulted in the isolation of a series of complexes with unusual composition and structure including complexes with a single Cp* ligand, multiple azide ligands, and bipy ligands with close parallel orientations. These results not only reveal new structural types, but they also show the diverse chemistry displayed by this redox‐active platform. Treatment of Cp*2NdCl(bipy) with excess KC8 resulted in the formation of the mono‐Cp* Nd(III) complex, [K(crypt)]2[Cp*Nd(bipy)2], 1, as well as [K(crypt)][Cp*2NdCl2], 2, and the previously reported [K(crypt)][Cp*2Nd(bipy)]. A mono‐Cp* Lu(III) complex, Cp*Lu(bipy)2, 3, was also found in an attempt to make Cp*2Lu(bipy) from LuCl3, 2 equiv. of KCp*, bipy, and K/KI. Surprisingly, the (bipy)1− ligands in neighboring molecules in the structure of 3 are oriented in a parallel fashion with intermolecular C⋅⋅⋅C distances of 3.289(4) Å, which are shorter than the sum of van der Waals radii of two carbon atoms, 3.4 Å. Another product with one Cp* ligand per lanthanide was isolated from the reaction of [K(crypt)][Cp*2Eu(bipy)] with azobenzene, which afforded the dimeric Eu(II) complex, [K(crypt)]2[Cp*Eu(THF)(PhNNPh)]2, 4. Attempts to make 4 from the reaction between Cp*2Eu(THF)2 and a reduced azobenzene anion generated instead the mixed‐valent Eu(III)/Eu(II) complex, [K(crypt)][Cp*Eu(THF)(PhNNPh)]2, 5, which allows direct comparison with the bimetallic Eu(II) complex 4. Mono‐Cp* complexes of Yb(III) are obtained from reactions of the Yb(II) complex, [K(crypt)][Cp*2Yb(bipy)], with trimethylsilylazide, which afforded the tetra‐azido [K(crypt)]2[Cp*Yb(N3)4], 6, or the di‐azido complex [K(crypt)]2[Cp*Yb(N3)2(bipy)], 7 a, depending on the reaction stoichiometry. A mono‐Cp* Yb(III) complex is also isolated from reaction of [K(crypt)][Cp*2Yb(bipy)] with elemental sulfur which forms the mixed polysulfido Yb(III) complex [K(crypt)]2[Cp*Yb(S4)(S5)], 8 a. In contrast to these reactions that form mono‐Cp* products, reduction of Cp*2Yb(bipy) with 1 equiv. of KC8 in the presence of 18‐crown‐6 resulted in the complete loss of Cp* ligands and the formation of [K(18‐c‐6)(THF)][Yb(bipy)4], 9. The (bipy)1− ligands of 9 are arranged in a parallel orientation, as observed in the structure of 3, except in this case this interaction is intramolecular and involves pairs of ligands bound to the same Yb atom. Attempts to reduce further the Sm(II) (bipy)1− complex, Cp*2Sm(bipy) with 2 equiv. of KC8 in the presence of excess 18‐crown‐6 led to the isolation of a Sm(III) salt of (bipy)2− with an inverse sandwich Cp* counter‐cation and a co‐crystallized K(18‐c‐6)Cp* unit, [K2(18‐c‐6)2Cp*]2[Cp*2Sm(bipy)]2 ⋅ [K(18‐c‐6)Cp*], 10. [ABSTRACT FROM AUTHOR]

This document discusses the use of electrochemical reduction reactions to convert carbon dioxide into useful chemical products, such as carbon monoxide and formic acid. The article explains that these reactions can be catalyzed either homogeneously or heterogeneously, and they offer a promising approach to finding alternatives to fossil fuels and reducing climate impact. The document also presents a method for conducting an experimental electrochemical CO2 reduction in a school setting, making it accessible for educational purposes. The research aims to emphasize the importance of sustainable energy and chemical production in addressing climate change. Additionally, the document describes an experiment using a tin electrode to reduce carbon dioxide and produce formate, and discusses the potential applications of this experiment in the context of climate change and the chemical industry. [Extracted from the article]

BACKGROUND: Improvements in farmland soil organic carbon (SOC) stock enhance crop yield and soil fertility while mitigating climate change. Rational fertilization in agricultural production is crucial for safeguarding SOC stock. In this study, field experiments were conducted with different ratios of chemical fertilizer reduction and organic fertilizer substitution for three consecutive years (2018--2020) to explore their effects and interlinkages on SOC fractions, soil properties and SOC stock. RESULTS: The results showed that organic fertilizer substitution increased SOC and its fractions content, SOC stock (by 3.98-- 12.98% and 7.15--18.13%) and soil fertility index (by 11.76--49.26% and 33.33--91.47%) compared to conventional fertilization in 2019 and 2020, while chemical fertilizer reduction had the opposite effect. Moreover, soil properties (except total nitrogen to total phosphorus ratio, N/P) and SOC fractions significantly affected SOC stock, with SOC fractions contributing more than soil properties. The high sensitivity of microbial biomass carbon (MBC) and dissolved organic carbon (DOC) can indicate changes in soil carbon pool. Structural equation modeling (SEM) revealed that organic fertilizer substitution increased SOC content and stock by increasing SOC fractions [recalcitrant organic carbon (ROC) and labile organic carbon (LOC) fractions] content and soil fertility. CONCLUSIONS: Our study revealed the corresponding mechanisms of the two fertilization modes affecting SOC stock changes. The use of organic fertilizer substitution is recommended to increase SOC stocks and soil fertility in wheat fields. [ABSTRACT FROM AUTHOR]

Silver nanoparticles have shown inhibitory capabilities and its use in battling viral infections are strengthened by its potent antibacterial activity. Notably, since it directly affects antiviral efficacy, the proper choice of synthesis process for making silver nanoparticles is a vital element to be taken into consideration. The synthesis of silver nanoparticles for the treatment of viral and bacterial infections involves creating silver particles at the nanoscale with unique antimicrobial properties. Various methods exist for synthesizing silver nanoparticles, including chemical reduction, green synthesis, and physical methods. Chemical reduction involves using reducing agents to convert silver ions into silver nanoparticles. Green synthesis employs reducing agents in an environmentally friendly manner. Physical methods rely on techniques such as laser ablation or thermal evaporation to produce silver nanoparticles. In order to provide technological guidance for choosing antiviral silver nanoparticle manufacturing methods, this paper introduces and explores alternative synthesis methods for creating silver nanoparticles. [ABSTRACT FROM AUTHOR]

Solid electrolyte interphase (SEI) makes the electrochemical window of aqueous electrolytes beyond the thermodynamics limitation of water. However, achieving the energetic and robust SEI is more challenging in aqueous electrolytes because the low SEI formation efficiency (SFE) only contributed from anion‐reduced products, and the low SEI formation quality (SFQ) negatively impacted by the hydrogen evolution, resulting in a high Li loss to compensate for SEI formation. Herein, we propose a highly efficient strategy to construct Spatially‐Temporally Synchronized (STS) robust SEI by the involvement of synergistic chemical precipitation‐electrochemical reduction. In this case, a robust Li3PO4‐rich SEI enables intelligent inherent growth at the active site of the hydrogen by the chemical capture of the OH− stemmed from the HER to trigger the ionization balance of dihydrogen phosphate (H2PO4−) shift to insoluble solid Li3PO4. It is worth highlighting that the Li3PO4 formation does not extra‐consume lithium derived from the cathode but makes good use of the product of HER (OH−), prompting the SEI to achieve 100 % SFE and pushing the HER potential into −1.8 V vs. Ag/AgCl. This energetic and robust SEI offers a new way to achieve anion/concentration‐independent interfacial chemistry for the aqueous batteries. [ABSTRACT FROM AUTHOR]

Solid electrolyte interphase (SEI) makes the electrochemical window of aqueous electrolytes beyond the thermodynamics limitation of water. However, achieving the energetic and robust SEI is more challenging in aqueous electrolytes because the low SEI formation efficiency (SFE) only contributed from anion‐reduced products, and the low SEI formation quality (SFQ) negatively impacted by the hydrogen evolution, resulting in a high Li loss to compensate for SEI formation. Herein, we propose a highly efficient strategy to construct Spatially‐Temporally Synchronized (STS) robust SEI by the involvement of synergistic chemical precipitation‐electrochemical reduction. In this case, a robust Li3PO4‐rich SEI enables intelligent inherent growth at the active site of the hydrogen by the chemical capture of the OH− stemmed from the HER to trigger the ionization balance of dihydrogen phosphate (H2PO4−) shift to insoluble solid Li3PO4. It is worth highlighting that the Li3PO4 formation does not extra‐consume lithium derived from the cathode but makes good use of the product of HER (OH−), prompting the SEI to achieve 100 % SFE and pushing the HER potential into −1.8 V vs. Ag/AgCl. This energetic and robust SEI offers a new way to achieve anion/concentration‐independent interfacial chemistry for the aqueous batteries. [ABSTRACT FROM AUTHOR]

This work reports that a low‐temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface‐active sites while maintaining the crystal morphology. All the experiments demonstrate that the new photocatalyst nano MIL‐125(Ti)‐250 obtained by thermal calcination strategy has abundant Ti3+ induced by oxygen vacancies and high specific surface area. This facilitates the adsorption and activation of N2 molecules on the active sites in the photocatalytic nitrogen fixation. The photocatalytic NH3 yield over MIL‐125(Ti)‐250 is enhanced to 156.9 μmol g−1 h−1, over twice higher than that of the parent MIL‐125(Ti) (76.2 μmol g−1 h−1). Combined with density function theory (DFT), it shows that the N2 adsorption pattern on the active sites tends to be from "end‐on" to "side‐on" mode, which is thermodynamically favourable. Moreover, the electrochemical tests demonstrate that the high atomic ratio of Ti3+/Ti4+ can enhance carrier separation, which also promotes the efficiency of photocatalytic N2 fixation. This work may offer new insights into the design of innovative photocatalysts for various chemical reduction reactions. [ABSTRACT FROM AUTHOR]

This work reports that a low‐temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface‐active sites while maintaining the crystal morphology. All the experiments demonstrate that the new photocatalyst nano MIL‐125(Ti)‐250 obtained by thermal calcination strategy has abundant Ti3+ induced by oxygen vacancies and high specific surface area. This facilitates the adsorption and activation of N2 molecules on the active sites in the photocatalytic nitrogen fixation. The photocatalytic NH3 yield over MIL‐125(Ti)‐250 is enhanced to 156.9 μmol g−1 h−1, over twice higher than that of the parent MIL‐125(Ti) (76.2 μmol g−1 h−1). Combined with density function theory (DFT), it shows that the N2 adsorption pattern on the active sites tends to be from "end‐on" to "side‐on" mode, which is thermodynamically favourable. Moreover, the electrochemical tests demonstrate that the high atomic ratio of Ti3+/Ti4+ can enhance carrier separation, which also promotes the efficiency of photocatalytic N2 fixation. This work may offer new insights into the design of innovative photocatalysts for various chemical reduction reactions. [ABSTRACT FROM AUTHOR]

Quorum sensing (QS) serves as a vital means of intercellular signalling in a variety of prokaryotes, which enables single cells to act in multicellular configurations. The potential to control community‐wide responses has also sparked numerous recent biotechnological innovations. However, our capacity to utilize intercellular communication is hindered due to a scarcity of complementary signalling systems and a restricted comprehension of interconnections between these systems caused by variations in their dynamic range. In this study, we utilize uniform manifold approximation and projection and extended‐connectivity fingerprints to explore the available chemical space of QS signalling molecules. We investigate and experimentally characterize a set of closely related QS signalling ligands, consisting of N‐acyl homoserine lactones and the aryl homoserine lactone p‐coumaroyl, as well as a set of more widely diverging QS ligands, consisting of photopyrones, dialkylresorcinols, 3,5‐dimethylpyrazin‐2‐ol and autoinducer‐2, and define their performance. We report on a set of six signal‐ and promoter‐orthogonal intercellular QS signalling systems, significantly expanding the toolkit for engineering community‐wide behaviour. Furthermore, we demonstrate that ligand diversity can serve as a statistically significant tool to predict much more complicated ligand‐receptor interactions. This approach highlights the potential of dimensionality reduction to explore chemical diversity in microbial dynamics. [ABSTRACT FROM AUTHOR]

Quorum sensing (QS) serves as a vital means of intercellular signalling in a variety of prokaryotes, which enables single cells to act in multicellular configurations. The potential to control community‐wide responses has also sparked numerous recent biotechnological innovations. However, our capacity to utilize intercellular communication is hindered due to a scarcity of complementary signalling systems and a restricted comprehension of interconnections between these systems caused by variations in their dynamic range. In this study, we utilize uniform manifold approximation and projection and extended‐connectivity fingerprints to explore the available chemical space of QS signalling molecules. We investigate and experimentally characterize a set of closely related QS signalling ligands, consisting of N‐acyl homoserine lactones and the aryl homoserine lactone p‐coumaroyl, as well as a set of more widely diverging QS ligands, consisting of photopyrones, dialkylresorcinols, 3,5‐dimethylpyrazin‐2‐ol and autoinducer‐2, and define their performance. We report on a set of six signal‐ and promoter‐orthogonal intercellular QS signalling systems, significantly expanding the toolkit for engineering community‐wide behaviour. Furthermore, we demonstrate that ligand diversity can serve as a statistically significant tool to predict much more complicated ligand‐receptor interactions. This approach highlights the potential of dimensionality reduction to explore chemical diversity in microbial dynamics. [ABSTRACT FROM AUTHOR]

The competition between the ytterbium endo‐atom and the pyridine exo‐molecules as nucleophiles interacting with the electron‐deficient 1H,4H‐1,4‐diborabuckminsterfullerene was studied using the quantum chemical DFT PBE0 method. The equilibrium structural parameters, dipole moments, IR spectra, and exothermic effects of the formation of the C58B2•Py2 adduct and the endohedral Yb@C58B2•Py2 complex were determined. The concept of the state of oxidation/reduction of an atom in a chemical compound has been clarified. The localization of the ytterbium(II) under a pair of equivalent carbon atoms bonded to boron(III) atoms is predicted. The introduction of ytterbium(II) into the adduct cavity weakens exo‐bonds with pyridine molecules without changing the oxidation state of boron(III). Each nitrogen atom retains a lone electron pair, coordinated by a boron(III). The ytterbium(II) endo‐atom retains 14 electrons in f states. [ABSTRACT FROM AUTHOR]

This paper explores the interaction of divalent [Sm(DippForm)2(thf)2] with substrates containing azo linkages. Treatment of [Sm(DippForm)2(thf)2] with trans‐azobenzene results in formation of mononuclear [Smlll(DippForm)2(Ph2N2)(thf)] ⋅ 3THF (1) or dinuclear [Smlll(DippForm)(Ph2N2)(thf)]2 ⋅ 4THF (2) and [Sm(DippForm)3] depending on the reaction stoichiometry, where azobenzene has undergone either a one or two electron reduction. These reactions parallel the corresponding reactions of [Sm(C5Me5)2(thf)2], but the coordination of [N2Ph2]− in 1 differs significantly from that of {Sm(C5Me5)2(Ph2N2)(thf)}. On the other hand, the structure of 2 is similar to that of the pentamethylcyclopentadienyl analogue. The reaction of [Sm(DippForm)2(thf)2] with 1H‐1,2,3‐benzotriazole also yielded a trivalent samarium complex containing benzotriazolate (btz), [Smlll(DippForm)2(btz)(thf)] ⋅ THF (3), and suggests more utilization of 1H‐1,2,3‐benzotriazole in divalent lanthanoid reduction chemistry is possible. [ABSTRACT FROM AUTHOR]

A low‐cost plasma‐chemical hybrid process (PCHP) is proposed for simultaneous NOx and SOx treatment. PCHP can be integrated into existing desulfurization reactors by combining plasma oxidation and chemical reduction. PCHP is applied to glass melting furnace emissions with limited denitration technology, achieving higher removal efficiencies of NO, NOx, and SO2 (43%, 38%, and 28%, respectively) by optimizing reductant spray and installation angles. PCHP also improves fuel consumption, with a 0.04 increase in air ratio reducing energy consumption by 3.6 kL/day (equivalent to 6.6 t(CO2)/day reduction). In addition, PCHP allows for the collection and reuse of treated SO2 as sodium sulfate particles, making it a suitable aftertreatment technology for glass manufacturing exhaust. [ABSTRACT FROM AUTHOR]

Merino wool, a highly abundant natural fabric, was successfully transformed into a valuable substrate for preparing easily recoverable catalyst materials by depositing gold nanoparticles (AuNPs) through a series of modification steps. The functionality of wool was enhanced by cleaving‐SH groups using NaHS chemical reduction. Subsequently, the reduced wool keratin (WSH) was covalently attached to 3‐amino thiophenol (3‐ATP) or 4‐amino thiophenol (4‐ATP) monomers via S−S linkages. The surface was further modified by grafting P3ATP or P4ATP through oxidative polymerization of 3‐ATP or 4‐ATP using ammonium persulfate as an oxidant. Finally, AuNPs were deposited onto the P3ATP or P4ATP‐grafted wool (P3ATP‐g‐WSH or P4ATP‐g‐WSH) by immersing the samples in an aqueous HAuCl4 solution. Additionally, P3ATP or P4ATP‐coated composites (P3ATP/WSH or P4ATP/WSH) were prepared to assess the AuNP formation ability of the grafting. The structural and morphological changes occurred in the wool, and the presence of AuNPs was revealed by ATR‐FTIR, XPS, SEM, and contact angle. The catalytic performance of the AuNP‐containing composites in reducing various nitroarenes to aminoarenes using an excess of electron‐donor (NaBH4) was monitored by UV‐vis spectroscopy. The developed composites demonstrated high efficiency, reusability, and rapid catalytic activity, achieving the highest apparent rate constant of 3.79 min−1, even within 1 min. [ABSTRACT FROM AUTHOR]

The reaction of benzoborirene with one equivalent of isocyanides leads to benzene‐fused boretes bearing one imine function, while the reaction with two equivalents of isocyanide affords 2,3‐dihydro‐2,3‐diiminoboroles with perfect regioselectivity. The isocyanide double insertion products represent a novel type of 1,2‐diimine with a benzoborole backbone. The reduction chemistry of the benzoborole‐supported 1,2‐diimine was investigated. Single‐ and two‐electron reduction allow for the isolation and full characterization of a radical anion and a dianion, respectively. In stark contrast to the ordinary boroles, which should turn aromatic by accepting two electrons, the antiaromatic character of the benzoborole backbone is highlighted upon reduction, thus presenting a rare example of antiaromatic borole dianion. Detailed quantum chemical calculations provide a rationale for the observed regioselectivity and the electronic structure of the reduced borole diimine species. [ABSTRACT FROM AUTHOR]

Constructing a stable solid electrolyte interphase (SEI) at the electrode–electrolyte interface is powerful for optimizing the battery performance. However, studies related to interface chemistry have particularly focused on engineering electrolytes and overlooked regulating electrode materials. Here, this study reports that the B‐doped Bi interconnected nanoparticles (B─Bi) are prepared by a facile and effective chemical reduction reaction. The B doping helps to catalyze the electrolyte decomposition and more NaF formation on the electrode surface, which facilitates a stable uniform SEI with enhanced mechanical stability. Such a robust SEI layer can inhibit the further decomposition of electrolytes and promote the interfacial Na+ transfer. The B─Bi offers a reversible capacity of 403.1 mAh g−1 at 1.0 A g−1 and a high rate capability of 203 mAh g−1 at 80 A g−1. Moreover, the B‐doping method also finds its viability to stabilize SEI in Sb material. This study demonstrates a new strategy for engineering the interface chemistry toward stable SEI and excellent performance. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction reaction (CO2RR) over Cu catalysts exhibits enormous potential for efficiently converting CO2 to ethylene (C2H4). However, achieving high C2H4 selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO2RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu‐based material to a pathway that facilitates CO2 reduction to C2H4 products. An excellent Faraday efficiency (FE) of 63.6 % on C2H4 with a current density of 497.2 mA cm−2 in flow cell was achieved, about 6.5 times higher than the pristine Cu catalyst which mainly produce CH4. The in situ X‐ray absorption spectroscopy and Raman studies reveal that the hydroxyl group in TA stabilizes Cuδ+ during the CO2RR. Furthermore, theoretical calculations demonstrate that the Cuδ+/Cu0 interfaces lower the activation energy barrier for *CO dimerization, and hydroxyl species stabilize the *COH intermediate via hydrogen bonding, thereby promoting C2H4 production. Such molecule engineering modulated electronic structure provides a promising strategy to achieve highly selective CO2 reduction to value‐added chemicals. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction reaction (CO2RR) over Cu catalysts exhibits enormous potential for efficiently converting CO2 to ethylene (C2H4). However, achieving high C2H4 selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO2RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu‐based material to a pathway that facilitates CO2 reduction to C2H4 products. An excellent Faraday efficiency (FE) of 63.6 % on C2H4 with a current density of 497.2 mA cm−2 in flow cell was achieved, about 6.5 times higher than the pristine Cu catalyst which mainly produce CH4. The in situ X‐ray absorption spectroscopy and Raman studies reveal that the hydroxyl group in TA stabilizes Cuδ+ during the CO2RR. Furthermore, theoretical calculations demonstrate that the Cuδ+/Cu0 interfaces lower the activation energy barrier for *CO dimerization, and hydroxyl species stabilize the *COH intermediate via hydrogen bonding, thereby promoting C2H4 production. Such molecule engineering modulated electronic structure provides a promising strategy to achieve highly selective CO2 reduction to value‐added chemicals. [ABSTRACT FROM AUTHOR]

We report the formation of a NpIV complex from the complexation of NpVIO22+ with the redox‐active ligand tBu‐pdiop2−=2,6‐bis[N‐(3,5‐di‐tert‐butyl‐2‐hydroxyphenyl)iminomethyl]pyridine. To the best of our knowledge, this is the first example of the direct complexation‐induced chemical reduction of NpVIO22+ to NpIV. In contrast, the complexation of UVIO22+ with tBu‐pdiop2− did not induce the reduction of UVIO22+, not even after the two‐electron electrochemical reduction of [UVIO2(tBu‐pdiop)]. This contrast between the Np and U systems may be ascribed to the decrease of the energy of the 5 f orbitals in Np compared to those in U. The present findings indicate that the redox chemistry between UVIO22+ and NpVIO22+ should be clearly differentiated in redox‐active ligand systems. [ABSTRACT FROM AUTHOR]

Autocatalytic reactions were proposed to play a key role at the beginning of life starting from the first reduction of CO2 to formate, acetate and C1−C4 hydrocarbons. In carbon capture and utilization (CCU) processes, the same reactions were demonstrated to be autocatalytic and, in some cases, promoted by catalysts of the same composition. Through evolution, CO2 reduction then turned into complex autocatalytic networks such as photosynthesis, where CCU chemists found inspiration for the development of more advanced systems for the synthesis of value‐added chemicals. Less evolved systems than photosynthesis, however, may be easier to emulate and provide valuable inspiration into CO2 reduction chemistry for CCU. Other synthetic systems were also demonstrated to be autocatalytic demonstrating that CO2 reactions and autocatalysis are closely connected. In this concept article, the relationship between natural, artificial and bio‐inspired autocatalytic CO2 reduction processes is summarized and discussed. The accomplishments resulting from the integration of autocatalysis and CCU strategies, along with their inherent benefits and future prospectives are also outlined. [ABSTRACT FROM AUTHOR]

In this study, a new concept of physical unclonable functions (PUFs) is introduced comprising reduced graphene oxide (GO) materials. To create a disordered conductivity distribution, two types of GO are used: HGO, are produced by the conventional Hummers' method, and PGO, produced by Brodie's method with an additional unique purification procedure. It is found that PGO becomes graphene-like after room-temperature chemical reduction. These two reduced GOs have a distinct conductivity difference of up to 104 times. By blending these two materials, a random mixture is created that can generate a highly unpredictable electrical signal, serving as an ideal security key with strong randomness and uniqueness. The optimized PUF device, based on this approach, demonstrates excellent performance in generating secure keys. [ABSTRACT FROM AUTHOR]

The complex [Mn(bpy)(CO)3Br], has been previously studied as both an electrocatalyst and a photocatalyst, in conjugation with a photosensitizer, for CO2 reduction to CO. This study considers the relationship between this catalytic activity and the steric and electronic nature of the aromatic diimine ligand. To this end, the π‐system in the bidentate ligand is increased step‐wise from 2,2′‐bipyridine (bpy) to 2‐(2‐pyridyl)quinoline (pq) to 2,2′‐biquinoline (bqn) in a series of three fac‐[Mn(α‐diimine)(CO)3Br] complexes. It is found that the propensity of these complexes to photochemically dimerize trends with the energy of the α‐diimine π* energy. Electrochemically, it is observed that the second reduction event in these systems becomes increasingly thermodynamically favorable and approaches the potential of the first reduction event as the π‐system expands. In fac‐[Mn(bqn)(CO)3Br], the second reduction is more favorable than the first reduction, precluding the formation of a dimer intermediate; even though, chemical reduction of fac‐[Mn(bqn)(CO)3Br] confirms that the dimer, [Mn(bqn)(CO)3Br]2 is able to form and not prevented by steric considerations. Though the second reduction potential is more positive for bqn and pq than for bpy, the CO2 reduction mechanism changes such that the overpotential for carbon dioxide reduction occurs at more negative potentials, leading to a decrease in overall catalytic activity. [ABSTRACT FROM AUTHOR]

Carbon use efficiency (CUE) is being intensively applied to quantify carbon (C) cycling processes from microbial cell to global scales. Energy use efficiency (EUE) is at least as important as the CUE because (i) microorganisms use organic C mainly as an energy source and not as elemental C per se, and (ii) microbial growth and maintenance are limited by energy, but not by C as a structural element. We conceptualize and review the importance of EUE by soil microorganisms and focus on (i) the energy content in organic compounds depending on the nominal oxidation state of carbon (NOSC), (ii) approaches to assess EUE, (iii) similarities and differences between CUE and EUE, and (iv) discuss mechanisms responsible for lower EUE compared to CUE. The energy content per C atom (enthalpy of combustion, the total energy stored in a compound) in organic compounds is very closely (R2 = 0.98) positively related to NOSC and increases by 108 kJ mol−1 C per one NOSC unit. For the first time we assessed the NOSC of microbial biomass in soil (−0.52) and calculated the corresponding energy content of −510 kJ mol−1 C. We linked CUE and EUE considering the NOSC of microbial biomass and element compositions of substrates utilized by microorganisms. The mean microbial EUE (0.32–0.35) is 18% lower than CUE (0.41) using glucose as a substrate. This definitely indicates that microbial growth is limited by energy relative to C. Based on the comparison of a broad range of processes of C and energy utilization for cell growth and maintenance, as well as database of experimental CUE from various compounds, we clearly explained five mechanisms and main factors why EUE is lower than CUE. The two main mechanisms behind lower EUE versus CUE are: (i) microbial recycling: C can be microbially recycled, whereas energy is always utilized only once, and (ii) chemical reduction of organic and inorganic compounds: Energy is used for reduction, which is ongoing without C utilization. [ABSTRACT FROM AUTHOR]

The detection of trace microRNAs (miRNA) is crucial for early cancer diagnosis. Here, a sensitive biosensor for miRNA directive detection was put forward, which was based on RNA‐templated palladium nanoparticles (PdNPs) signal amplification strategy. Uncharged peptide nucleic acids (PNA) probe was used to capture the target miRNA(T‐RNA) specifically. Subsequently, a large amount of palladium ions absorbed on T‐RNA strands via electrostatic forces, and the palladium nanocluster is rapidly generated based on chemical reduction. Obviously, RNA metallization method enables biosensor to be carried out efficiently at room temperature also simplifies the preparation and detection of the sensor. Under optimal conditions, this method can analyze the concentration of miRNA in the range of 10 fM to 1 nM, and the detection limit is 3.33 fM. At the same time, this method has strong anti‐interference ability in serum samples, which provides a broad prospect for the early screening and diagnosis of cancer. [ABSTRACT FROM AUTHOR]

Massive efforts are invested in developing innovative CO2‐sequestration strategies to counter climate change and transform CO2 into higher‐value products. CO2‐capture by reduction is a chemical challenge, and attention is turned toward biological systems that selectively and efficiently catalyse this reaction under mild conditions and in aqueous solvents. While a few reports have evaluated the effectiveness of isolated bacterial formate dehydrogenases as catalysts for the reversible electrochemical reduction of CO2, it is imperative to explore other enzymes among the natural reservoir of potential models that might exhibit higher turnover rates or preferential directionality for the reductive reaction. Here, we present electroenzymatic catalysis of formylmethanofuran dehydrogenase, a CO2‐reducing‐and‐fixing biomachinery isolated from a thermophilic methanogen, which was deposited on a graphite rod electrode to enable direct electron transfer for electroenzymatic CO2 reduction. The gas is reduced with a high Faradaic efficiency (109±1 %), where a low affinity for formate prevents its electrochemical reoxidation and favours formate accumulation. These properties make the enzyme an excellent tool for electroenzymatic CO2‐fixation and inspiration for protein engineering that would be beneficial for biotechnological purposes to convert the greenhouse gas into stable formate that can subsequently be safely stored, transported, and used for power generation without energy loss. [ABSTRACT FROM AUTHOR]

Upgrading cyclohexanone to ϵ‐caprolactone (ϵ‐CL) is of great importance to the synthesis of high value‐added downstream chemicals and the reduction of foam plastic. The catalytic synthesis of ϵ‐CL from cyclohexanone through O2/aldehyde method is an environmentally benign one‐pot tandem reaction without using peroxy acid, balancing the requirements of safety and efficiency. However, due to lack of elaborate design and collaboration of multiple active sites for catalysts, the catalytic efficiency of O2/aldehyde method still remains to be improved. Herein, a pitaya‐like catalyst (CeFe@RDC‐3) with Ce and Fe highly dispersed on resin‐derived‐carbon is synthesized through high temperature self‐assembly. On this bimetallic catalyst, high yield (97 %) of ϵ‐CL is achieved through aerobic oxidation of cyclohexanone with only 1.5 equivalent benzaldehyde. Moreover, considerable yields of ϵ‐CL, 88.3 % and 74.7 %, respectively, are also obtained over CeFe@RDC‐3 with green solvent (EtOAc) or even without solvent. No loss of activity is observed after five successive cycles, demonstrating high stability of CeFe@RDC‐3. The mechanism study reveals that the high performance of CeFe@RDC‐3 is ascribed to the Ce−Fe bimetallic synergy, uniform metal dispersion, abundant active oxygen and stabilizing effect of resin‐derived‐carbon to free radicals. This work provides prospect for a green, safe and low‐cost strategy for Baeyer‐Villiger process. [ABSTRACT FROM AUTHOR]

Massive efforts are invested in developing innovative CO2‐sequestration strategies to counter climate change and transform CO2 into higher‐value products. CO2‐capture by reduction is a chemical challenge, and attention is turned toward biological systems that selectively and efficiently catalyse this reaction under mild conditions and in aqueous solvents. While a few reports have evaluated the effectiveness of isolated bacterial formate dehydrogenases as catalysts for the reversible electrochemical reduction of CO2, it is imperative to explore other enzymes among the natural reservoir of potential models that might exhibit higher turnover rates or preferential directionality for the reductive reaction. Here, we present electroenzymatic catalysis of formylmethanofuran dehydrogenase, a CO2‐reducing‐and‐fixing biomachinery isolated from a thermophilic methanogen, which was deposited on a graphite rod electrode to enable direct electron transfer for electroenzymatic CO2 reduction. The gas is reduced with a high Faradaic efficiency (109±1 %), where a low affinity for formate prevents its electrochemical reoxidation and favours formate accumulation. These properties make the enzyme an excellent tool for electroenzymatic CO2‐fixation and inspiration for protein engineering that would be beneficial for biotechnological purposes to convert the greenhouse gas into stable formate that can subsequently be safely stored, transported, and used for power generation without energy loss. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g. ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g. ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR. [ABSTRACT FROM AUTHOR]