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Tandem hydroformylation/hydrogenation of olefins to alcohols is an appealing and challenging route that has received continuous interest. Herein, we report a bifunctional atomically dispersed Rh and Co catalyst (RhCo/Al2O3-10) prepared by a simple ball milling method that displays superior synergistic catalytic performance (>95% olefins conversion and >80% alcohols selectivity) and broad substrate scope for tandem hydroformylation/hydrogenation reaction, outperforming Rh/Al2O3, Co/Al2O3, and their physically mixed counterparts. In situ CO-DRIFTS, XPS, and kinetic experiments demonstrate that the electron interaction between Rh and Co atoms effectively lowers the apparent activation energy, thus promoting the tandem hydroformylation/hydrogenation reaction. This work not only presents a novel tandem hydroformylation/hydrogenation reaction system for converting olefins to alcohol but also throws light on the rational design of versatile bifunctional catalysts for on-demand synergistic catalysis. [ABSTRACT FROM AUTHOR]

The quest for sustainable synthesis of carboxylic acids has led to the exploration of innovative routes and catalysts for the oxidative cleavage of carbon−carbon double bonds, prevalent in bio‐derived molecules. This process involves multiple steps including epoxidation, hydrolysis and vicinal diol cleavage, often catalysed by unsustainable homogeneous or noble‐metal catalysts. In this study, we present the utilization of Fe‐ZSM‐5 as a versatile bifunctional catalyst capable of catalysing both hydrolysis and vicinal diol cleavage steps, utilizing propylene oxide as model compound and H2O2 as oxidizing agent. The prepared Fe‐ZSM‐5 features the zeolite intrinsic Lewis and Brønsted acidity functions, essential for the hydrolysis step, as well as high fractions of monomeric FeOx species, crucial for the subsequent vicinal diol cleavage, leading to streamlined carboxylic acids formation in a one‐pot, two‐step process. Moreover, by combining Fe‐ZSM‐5 with TS‐1, renowned for its epoxidation activity, we demonstrate the complete cascade reaction in one pot, under mild conditions, starting from ethylene. Our study expands the utility of cost‐effective zeolite‐based catalysts enriched with abundant Fe metal for the one‐pot oxidative cleavage of C=C double bonds, offering a promising pathway towards sustainable carboxylic acid synthesis. [ABSTRACT FROM AUTHOR]

Seawater electrolysis is an innovative technique that can potentially transform hydrogen production and contribute to environmental redemption. However, the lack of good bifunctional electrocatalysts may hinder further development of this technology. Herein, nickel hydroxide nanosheets can be employed as a precursor to producing a 3D Prussian blue analogue (PBA) with a distinct dimensional structure. Nickel hydroxide nanosheets are formed within a nickel foam and undergo a reaction with potassium ferricyanide (K3[Fe(CN)6]). The nickel hydroxide structure is sheets‐like and well‐preserved, containing a multitude of PBA nanocubes. Following phosphidation at 350 °C, the iron‐doped nickel phosphide (Fe‐doped Ni2P (1.0 mM) nanosheets) demonstrates remarkable potential as a bifunctional electrocatalyst for total water/seawater splitting. This electrocatalyst demonstrates exceptional performance in overall water splitting, achieving current densities of 100 and 500 mA cm−2 in 1.0 M KOH at remarkably low voltages of 1.65 and 2.06 V, respectively. Additionally, its improved ability to resist corrosion and its hydrophilic surface makes it suitable for the seawater splitting process. The material can generate current densities of 100 to 500 mA cm−2 in seawater with 1.0 M KOH, resulting in voltages of 1.74 and 2.32 V. These outstanding results, together with its durability, indicate the material's strong potential for practical seawater electrolysis. [ABSTRACT FROM AUTHOR]

Biomass valorisation through the selective oxidation of carbohydrate and lipid derivatives offers access to an array of platform chemicals through energy- and atom-efficient catalytic processes. Supported metal nanoparticles are promising catalysts for the aerobic selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), but typically require strong liquid base to achieve high selectivity. Here, we explore the utility of MgO as a solid base support for the Ru-catalysed aerobic oxidation of HMF, obtaining 68% FDCA yield at 160°C and 1.5 MPa of O2 using <1 mol-% metal. Biomass offers a sustainable alternative source of carbon to existing fossil resources that underpin the global chemical industry – on which we rely for fuels, plastics and pharmaceuticals. Combining ruthenium metal with Earth-abundant magnesium oxide creates an efficient catalyst for transforming sugar components of waste biomass into a valuable precursor for the sustainable manufacture of plastics. (Image credit: Priya Lokhande.) This article belongs to the 10th Anniversary Collection of RACI and AAS Award papers. [ABSTRACT FROM AUTHOR]

Fabrication of highly efficient and earth-abundant bifunctional electrocatalyst to accelerate the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are critical for overall water splitting. In this work, bimetallic Co/Mo oxides modified reduced graphene oxide (rGO) was synthesized using a simple one-pot hydrothermal method, which significantly improved the electrocatalytic activity in both HER and OER. Under the optimal conditions, the double layer capacitance of rGO modified by Co/Mo bimetal is 78.08 mF cm−2. The overpotential required for HER to reach -10 mA cm−2 current density is 488 mV, the dynamic Tafel slope is 126 mV dec−1. The overpotential required for OER to reach 10 mA cm−2 current density is 420 mV, the slope of kinetic Tafel is 169 mV dec−1. This work provides a new prospect for the rational design and fabrication of efficient HER/OER bifunctional electrocatalysts in electrochemical energy device application. [ABSTRACT FROM AUTHOR]

Copyright of Rare Metals is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

To find a solution to the global energy demand, efficient energy production and storage devices are utmost required. Taking advantage of the unique combination of hydrophilicity and conductivity of MXene, a bifunctional nonnoble metal-based electrode NiCo2O4/NiO/MXene (CNOT) is developed. Low conductivity and aggregation of transition metal oxides are compensated by making a hybrid of NiCo2O4/NiO with MXene. CNOT, as an anode catalyst in direct methanol fuel cell (DMFC), offers methanol oxidation reaction current density of 15A/g and low onset potential. Symmetric supercapacitor developed using CNOT in 3M KOH solution offers 0.9V potential window, and 32.66Fg−1 specific capacitance at 2.5A/g. Whereas, symmetric supercapacitor CNOT//CNOT in PVA/KOH hydrogel polymer electrolyte provides a broader window of 1.4V, with specific capacitance of 87.331Fg−1, and very high energy and power density of 23.77Wh/kg and 1808.87W/kg, respectively, at 2.5A/g. The hydrogel polymer electrolyte (PVA/KOH) outperforms aqueous 3M KOH by providing a larger window, higher capacitance, excellent energy and power density. Thus, the hybrid electrode provides synergistic effects of the electro-active NiCo2O4, NiO and MXene nanosheets and exhibits versatility in DMFC and symmetric supercapacitor. [ABSTRACT FROM AUTHOR]

Copyright of Rare Metals is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Green and sustainable energy alternatives to replace fossil fuels are a topic of research in scientific community, thus yielding pursuit of advancing renewable energy systems with hydrogen emerging as a suitable and viable alternative. Efficient and non‐precious metal catalysts are crucial for large‐scale electrochemical water splitting yielding clean H2. Here, a novel two‐step hydrothermal synthesis approach to fabricate manganese–cobalt selenide nano‐cubes grown directly on nickel foam (NF) (MnCo2Se4/NF) is adopted. Leveraging its hierarchically structured architecture, augmented active sites, and electrochemically active surface area, MnCo2Se4/NF material demonstrates exceptional electrocatalytic performance for both water oxidation and reduction. With an overpotential of 233 mV for oxygen evolution reaction (OER) and 187 mV for hydrogen evolution reaction at a current density of 10 mA/cm2, MnCo2Se4/NF also exhibits a Tafel slope of 44 mV/dec for sluggish OER process. Notably, this nanocrystalline catalyst displays enhanced catalytic activity under alkaline conditions, accelerates water dissociation, and maintains good stability over 50 h. Outperforming state‐of‐the‐art RuO2, particularly in two‐electrode assemblies with an overpotential of 218 mV at 10 mA/cm2, this work offers a promising pathway for designing and manufacturing of innovative bifunctional electrocatalysts for efficient water splitting processes, thereby contributing to broader goal of sustainable energy production. [ABSTRACT FROM AUTHOR]

Noble metal nanoparticles incorporated in hybrid nanocomposites are considered as promising candidates for electrochemical applications owing to their physicochemical properties. In this work, we demonstrated the preparation of Fe2O3/rGO nanocomposite by hydrothermal method, followed by in situ Ag binding synthesis for the fabrication of hybrid nanocomposite (Ag/α-Fe2O3/rGO). The crystallographic structure of the hybrid nanocomposite is examined by X-ray diffraction (XRD) analysis which confirms the characteristics of Ag, Fe2O3, and rGO. The microscopic studies and energy-dispersive X-ray analysis (EDS) spectra confirmed the presence and formation of hybrid nanostructures. Raman analysis results further corroborate the formation of composite with significant D and G bands in Fe2O3/rGO and Ag/α-Fe2O3/rGO samples, which follow XRD results. Cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) studies were carried out to analyze the faradaic capacitor behavior. A specific capacitance of 209.09 F/g was observed by GCD studies for Ag/α-Fe2O3/rGO composites at a current density of 1 A/g, which exhibited good capacitance retention of 94% for 5000 cycles at 7 A/g. Furthermore, the Ag/α-Fe2O3/rGO electrode was used for the electrochemical detection of nitrate ions in soil by utilizing an ion-selective membrane over the surface of the Ag/α-Fe2O3/rGO electrode. The fabricated nanocomposite electrode showed a significant change in the peak current values with the concentration of nitrate in a linear range from 10 to 450 μM with the sensitivity to be calculated 1.426 μA μM−1 cm−2 and limit of detection (LOD) calculated to be 0.18 μM. The reproducibility and interference studies showed a promising result to be utilized for detecting nitrate ions in soil and in real-time applications. [ABSTRACT FROM AUTHOR]

Lithium‐sulfur (Li−S) batteries, recognized as one of the most promising next‐generation energy storage systems, are still limited by the “shuttle effect” of soluble polysulfides (LiPSs) on the cathode and the uncontrolled growth of lithium dendrites on the anode. These issues are critical obstacles to their practical application. Currently, many researchers have addressed these challenges from a unilateral perspective. Herein, we propose bifunctional hosts based on high‐entropy selenides (HE−Se) to simultaneously tackle the persistent problems on both the positive and negative electrodes of Li−S batteries. On the one hand, HE−Se interacts with polysulfides to promote their conversion, effectively mitigating the shuttle effect. On the other hand, HE−Se provides multiple lithophilic sites during the initial nucleation of Li+, which reduces overpotential and exhibits excellent lithophilicity and cyclic stability. As a result, Li−S batteries incorporating the HE−Se hosts demonstrate outstanding performance in terms of rate capability and cycling stability. Additionally, the porous lithophilic HE−Se structure offers sufficient nucleation sites, inhibits the growth of dendritic lithium, and accommodates volume changes during charging and discharging cycles. This study highlights the potential of sulphophilic/lithophilic high‐entropy materials in designing advanced Li−S batteries and encourages further exploration in this area. [ABSTRACT FROM AUTHOR]

The design of bifunctional electrocatalysts toward reduction reaction of carbon dioxide (ECO2RR) and oxygen evolution reaction (OER) in aqueous rechargeable Zn─CO2 batteries (ZABs) still poses a significant challenge. Herein, Ni clusters (Nix) of 0.5 and 0.8 nm in diameter coupled with single Ni site (Ni−N4−C), denoted as Ni−N4/Ni5 and Ni−N4/Ni8, respectively, are synthesized and the size effect of Ni nanoclusters are studied. Ni−N4/Ni5 exhibits an ≈100% Faradaic efficiency (FECO) toward ECO2RR for CO from −0.4 to −0.8 V versus the reversible hydrogen electrode, superior to that of Ni−N4−C (FECO = 55.0%) and Ni−N4/Ni8 (FECO = 80.0%). The OER performance of Ni−N4/Ni5 and Ni−N4/Ni8 are superior or comparable to that of commercial RuO2 but outperform that of Ni−N4−C. Theoretical calculation indicates that *COOH of ECO2RR intermediates bond synergistically with Nix clusters and Ni−N4−C single atom site, promoting the activation of CO2 and reducing the energy barrier of the potential determining step of ECO2RR. Such effect is strongly size‐dependent and larger Nix nanoclusters result in too strong binding of *COOH intermediates, impede the formation of *CO. As a bifunctional cathode electrocatalyst of rechargeable alkaline aqueous ZABs, Ni−N4/Ni5 exhibits a peak power density of 11.7 mW cm−2 and cycling durability over 1200 cycles and 420 h. [ABSTRACT FROM AUTHOR]

The design and synthesis of polyhedra using coordination‐driven self‐assembly has been an intriguing research area for synthetic chemists. Metal‐organic polyhedra are a class of intricate molecular architectures that have garnered significant attention in the literature due to their diverse structures and potential applications. Hereby, we report Cu‐MOP, a bifunctional metal‐organic cuboctahedra built using 2,6‐dimethylpyridine‐3,5‐dicarboxylic acid and copper acetate at room temperature. The presence of both Lewis basic pyridine groups and Lewis acidic copper sites imparts catalytic activity to Cu‐MOP for the tandem one‐pot deacetalization‐Knoevenagel/Henry reactions. The effect of solvent system and time duration on the yields of the reactions was studied, and the results illustrate the promising potential of these metal‐organic cuboctahedra, also known as nanoballs for applications in catalysis. [ABSTRACT FROM AUTHOR]

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers. [ABSTRACT FROM AUTHOR]

The pursuit of efficient and durable bifunctional electrocatalysts for overall water splitting in acidic media is highly desirable, albeit challenging. SrIrO3 based perovskites are electrochemically active for oxygen evolution reaction (OER), however, their inert activities toward hydrogen evolution reaction (HER) severely restrict the practical implementation in overall water splitting. Herein, an Ir@SrIrO3 heterojunction is newly developed by a partial exsolution approach, ensuring strong metal‐support interaction for OER and HER. Notably, the Ir@SrIrO3‐175 electrocatalyst, prepared by annealing SrIrO3 in 5% H2 atmosphere at 175 °C, delivers ultralow overpotentials of 229 mV at 10 mA cm−2 for OER and 28 mV at 10 mA cm−2 for HER, surpassing most recently reported bifunctional electrocatalysts. Moreover, the water electrolyzer using the Ir@SrIrO3‐175 bifunctional electrocatalyst demonstrates the potential application prospect with high electrochemical performance and excellent durability in acidic environment. Theoretical calculations unveil that constructing Ir@SrIrO3 heterojunction regulates interfacial electronic redistribution, ultimately enabling low energy barriers for both OER and HER. [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) is a complex multifactorial neurodegenerative disease. Metal ion dyshomeostasis and Aβ aggregation have been proposed to contribute to AD progression. Metal ions can bind to Aβ and promote Aβ aggregation, and ultimately lead to neuronal death. Bifunctional (metal chelation and Aβ interaction) compounds are showing promise against AD. In this work, eleven new 3,3'-diamino-2,2'-bipyridine derivatives 4a-4k were synthesized, and evaluated as bifunctional agents for AD treatment. In vitro Aβ aggregation inhibition assay confirmed that most of the synthesized compounds exhibited significant self-induced Aβ1−42 aggregation inhibition. Among them, compound 4d displayed the best inhibitory potency of self-induced Aβ1−42 aggregation with IC50 value of 9.4 µM, and it could selectively chelate with Cu2+ and exhibited 66.2% inhibition of Cu2+-induced Aβ1−42 aggregation. Meanwhile, compound 4d showed strong neuroprotective activity against Aβ1−42 and Cu2+-treated Aβ1−42 induced cell damage. Moreover, compound 4d in high dose significantly reversed Aβ-induced memory impairment in mice. [ABSTRACT FROM AUTHOR]

Heterojunction structures improve the intrinsic activity of electrocatalysts by enhancing the charge transfer between the catalyst and the electrode. In this paper, the NiS/FeS2 heterostructured electrocatalyst is fabricated by a simple sulfidation method using an interface engineering strategy to adjust the surface electron density of the electrocatalyst. As expected, NiS/FeS2 electrocatalyst exhibits superior activity and durable oxygen evolution reaction (OER) stability, requiring only a low overpotential of 183 mV to achieve a current density of 10 mA·cm−2 and can be stable for more than 80 h, superior to NiS, FeS2 electrocatalyst individually, and precious RuO2. Notably, NiS/FeS2 is also a good bifunctional electrocatalyst with good overall water splitting performance, and it only requires a voltage 1.56 V to obtain a current density of 10 mA·cm−2 for more than 12 h. Remarkably, the NiS/FeS2 hybridization facilitates the formation of coral-like structures, increasing the electrochemical surface area (ECSA) and enhancing the charge transfer efficiency, thus leading to excellent electrocatalytic performance. This work proposes a constructive strategy for designing efficient electrocatalysts based on interface engineering, and lays a foundation for designing a new class of electrocatalysts. [ABSTRACT FROM AUTHOR]

Atherosclerosis is a significant contributor to global cardiovascular disease. Reducing the formation of atherosclerotic plaque effectively can lead to a decrease in cardiovascular diseases. Therefore, controlling macrophage function is crucial. This study presents the creation of a bifunctional nanoparticle that is specific to macrophages to achieve intracellular and extracellular synergistic therapy for restoring macrophage functions. The nanoparticle is conjugated with anti-CD47 antibody to modulate extracellular CD47-SIRPα phagocytic signaling axis on the outer surface of macrophages and encapsulates the NLRP3 inhibitor (CY-09) to regulate intracellular inflammation response of macrophages. The results showed that the nanoparticles accumulate in the atherosclerotic plaque, alter macrophage phagocytosis, inhibit NLRP3 inflammasome activation, and decrease the plaque burden in Apoe−/− mice whilst ensuring safety. Examination of single-cell RNA sequencing indicates that this multifunctional nanoparticle decreases the expression of genes linked to inflammation and manages inflammatory pathways in the plaque lesion. This study proposes a synergistic therapeutic approach that utilizes a bifunctional nanoparticle, conjugated with anti-CD47, to regulate the microenvironment of plaques.

Developing highly efficient and low-cost hydrogen evolution reaction (HER) electrocatalysts is an urgent and important task for development of green water electrolysis hydrogen production technology. In this work, the nanostructured MoSe2/NiSe2 electrocatalyst with heterojunctions is constructed by a two-step hydrothermal method for HER coupling urea oxidation reaction (UOR). The presence of heterojunctions accelerates the charge transfer and enhances the conductivity of electrocatalysts; thus, the as-prepared nanostructured MoSe2/NiSe2 exhibits bifunctional electrocatalytic activity. Low overpotentials of 79 and 120 mV are required to achieve 10 mA cm–2 current density for the HER and UOR, respectively. For the two-electrode urea electrolysis containing 1 M KOH and 0.5 M urea, a voltage of only 1.47 V is required to deliver the current density of 10 mA cm–2. Density functional theory (DFT) calculation results show that the MoSe2/NiSe2 electrocatalyst can optimize the adsorption of H* and improve the HER activity because of the existence of the heterostructure. This work provides a promising potential for designing energy-saving hydrogen evolution catalysts with alternative electrode reactions. [ABSTRACT FROM AUTHOR]

The selective catalytic oxidation (SCO) is an effective method for removing slipped high-concentration ammonia from NH3-fueled engine exhaust gas. Herein a novel bifunctional catalyst was synthesized by mechanically mixing sulfated Ce/ZrO2 (Ce/ZrO2-S) with a small fraction of Pt/Al2O3 (Pt 0.1 wt.%) for SCO of NH3. As expected, the introduction of a small amount of Pt/Al2O3 significantly improved NH3 conversion ability of Ce/ZrO2-S catalysts toward low-temperature direction. When the mass ratio of Pt/Al2O3 to Ce/ZrO2-S was 7.5% (the corresponding mixed catalyst was denoted as P@CZS-7.5), T90 temperature was 312 °C. More importantly, P@CZS-7.5 catalyst exhibited a much better N2 selectivity (> 96%) in a wide temperature range (320 ~ 450 °C). H2-TPR results revealed that the addition of a trace amount of Pt/Al2O3 significantly led to a distinct shift of reduction temperature peak toward low-temperature direction, thereby greatly improved the low-temperature redox performance of mixed catalysts. Furthermore, NH3-TPD and BET results showed that P@CZS-7.5 catalyst exhibited a similar NH3 adsorption capacity to Ce/ZrO2-S catalyst, while the former had a relatively higher specific surface area than the latter. It was considered as a crucial factor for P@CZS-7.5 catalyst maintaining superior N2 selectivity in high-concentration NH3 (5000 ppm) removal processes. In situ DRIFTS results indicated that P@CZS-7.5 catalyst followed the internal selective catalytic reduction (i-SCR) mechanism in NH3-SCO reactions. [ABSTRACT FROM AUTHOR]

Introduction: The aim of the study was to compare maximal force, force steadiness, and the discharge characteristics of motor units in the tibialis anterior (TA) muscle during submaximal isometric contractions for ankle dorsiflexion and adduction of the foot. Methods: Nineteen active young adults performed maximal and submaximal isometric dorsiflexion and adduction contractions at five target forces (5%, 10%, 20%, 40%, and 60% maximal voluntary contraction [MVC]). The activity of motor units in TA was recorded by high-density EMG. Results: The maximal force was similar between dorsiflexion and adduction, despite EMG amplitude for TA being greater (P < 0.05) during dorsiflexion than adduction. The coefficient of variation (CV) for force (force steadiness) during dorsiflexion was always less (P < 0.05) than during adduction, except of 5% MVC force. No differences were observed for mean discharge rate; however, the regression between the changes in discharge rate relative to the change of force was significant for dorsiflexion (R² = 0.25, P < 0.05) but not for adduction. Discharge variability, however, was usually less during dorsiflexion. The CV for interspike interval was less (P < 0.05) at 10%, 20%, and 40% MVC but greater at 60% MVC during dorsiflexion than adduction. Similarly, the SD values of the filtered cumulative spike train of the motor units in TA were less (P < 0.05) at 5%, 10%, 20%, and 40% MVC during dorsiflexion than adduction. Conclusions: Although the mean discharge rate of motor units in TA was similar during foot adduction and ankle dorsiflexion, discharge variability was less during dorsiflexion resulting in less accurate performance of the steady adduction contractions. The neural drive to bifunctional muscles differs during their accessory function, which must be considered for training and rehabilitation interventions. [ABSTRACT FROM AUTHOR]

With the increasing environmental pollution and the depletion of non-renewable resources, it is very important for developing clean and renewable energy. The technology of water-splitting is an efficient and pollution-free method for producing hydrogen and oxygen, which is via two processes of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, the commercial precious metal catalyst has expensive cost and low abundance on earth. Therefore, it is very meaningful for developing the non-noble metal electrocatalysts with lower prices, high activity and stable performance. In this study, a series of nanoflower bifunctional electrocatalysts (CuSe2-CoSe2 (1∶1)NF, CuSe2 -CoSe2 (3∶1)NF and CuSe2 -CoSe2 (1∶3) NF) were successfully prepared by hydrothermal method. The structure, morphology, elemental composition and valence state of CuSe2 -CoSe2 NF catalyst were analyzed by a series of characterizations. The result shows that the existence of synergistic between CoSe2 and CuSe2 in CuSe2 -CoSe2 NF bimetallic selenide catalyst can accelerate the electron transfer and enhance the water-splitting performance. In addition, the CuSe2 -CoSe2 NF catalyst with nanoflower structure has large specific surface area (808 m2 / g), which can expose more active sites and further increase the electrochemical performance. Consequently, the CuSe2 -CoSe2 (1∶1)NF catalyst needs 42 and 204 mV overpotentials for HER and OER at 10 mA·cm-2 current density in 1 mol/L KOH electrolyte. The stability could maintain 100 h. The CuSe2 -CoSe2 (1∶1)NF performance is close to that of commercial Pt/ C and RuO2. [ABSTRACT FROM AUTHOR]

Carbon-supported noble-metal-free single-atom catalysts (SACs) have aroused widespread interest due to their green chemistry aspects and excellent performances. Herein, we propose a "ligand regulation strategy" and achieve the successful fabrication of bifunctional SAC/MOF (MOF = metal–organic framework) nanocomposite (abbreviated NiSA/ZIF-300; ZIF = ZIF-8) with exceptional catalytic performance and robustness. The designed NiSA/ZIF-300 has a planar interfacial structure with the Ni atom, involving one S and three N atoms bonded to Ni(II), fabricated by controllable pyrolysis of volatile Ni-S fragments. For CO2 cycloaddition to styrene epoxide, NiSA/ZIF-300 exhibits ultrahigh activity (turnover number (TON) = 1.18 × 105; turnover frequency (TOF) = 9830 molSC·molNi−1·h−1; SC = styrene carbonate) and durability at 70 °C under 1 atm CO2 pressure, which is much superior to Ni complex/ZIF, NiNP/ZIF-300, and most reported catalysts. This study offers a simple method of bifunctional SAC/MOF nanocomposite fabrication and usage, and provides guidance for the precise design of additional original SACs with unique catalytic properties. [ABSTRACT FROM AUTHOR]

Pd-based metallic nanosheets with advanced physicochemical properties have been widely prepared and employed in various electrocatalytic reactions. However, few concerns were focused on their multiple performances in different electrocatalysis. Here, highly curved and ultrathin PdNiRu nanosheets (NSs) are developed by facile wet-chemistry strategy and exhibit excellent electrocatalytic performance toward both oxygen reduction reaction (ORR) and ethylene glycol oxidation reaction (EGOR). Owing to the synergistically structural (e.g., ultrathin, curved, defects/steps-rich) and compositional (ternary alloy) advantages, PdNiRu NSs exhibited enhanced ORR and EGOR specific/mass activities and better stability/durability than control electrocatalysts. The specific activity (5.52 mA·cm−2) and mass activity (1.13 A·mgPd−1) of the PdNiRu NSs in ORR are 4.8 and 3.4 times as the ones of commercial Pt/C, respectively. The mass activity of PdNiRu NSs (3.86 A·mgPd−1) in EGOR is 2.6 times as commercial Pd/C (1.51 A·mgPd−1). This study is helpful for the development of desired electrocatalysts with multi-functional application in practical fuel cells. [ABSTRACT FROM AUTHOR]

A broadly improved second generation catalytic two‐phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting of a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization of prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows for divergent access to a wide range of C‐, N‐, O‐ and S‐ substituted P(V) containing compounds from a handful of enantioenriched intermediates. A new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed for a far wider substrate scope and increased reaction efficiency and practicality over previously established protocols. The resulting enantioenriched intermediates could then be transformed into an even greater range of distinct classes of P(V) compounds by displacement of the remaining leaving group as well as allowing for even further diversification downstream. Density functional theory (DFT) calculations were performed to pinpoint the origin of enantioselectivity for the BIMP‐catalyzed desymmetrization, to rationalize how a superior catalyst/leaving group combination leads to increased generality in our second‐generation catalytic system, as well as shed light onto observed stereochemical retention and inversion pathways when performing late‐stage enantiospecific SN2@P reactions with Grignard reagents. [ABSTRACT FROM AUTHOR]

Developing nonprecious metal-based bifunctional electrocatalysts toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) with low cost, high efficiency, and long-term stability is of great significance for alkaline electrolytic water splitting. In this work, a CeO2/(NiFe)3Se4 heterostructure is prepared by chemical deposition on the surface of (NiFe)3Se4 nanoarrays grown on nickel–iron foam (CeO2/(NiFe)3Se4/NIFs). The CeO2/(NiFe)3Se4/NIFs electrocatalysts exhibit a low OER overpotential of only 140 mV at 10 mA cm–2 and a high stability of 300 h at 230 mA cm–2, while an HER overpotential of 74 mV at 10 mA cm–2 is obtained. In addition, the CeO2/(NiFe)3Se4/NIF||CeO2/(NiFe)3Se4/NIF bipolar electrolytic cell needs only a voltage of 1.493 V at 10 mA cm–2, which is comparable to that of commercial Pt/C/NIF||IrO2/NIF bipolar electrolytic cells and superior to that of (NiFe)3Se4/NIF||(NiFe)3Se4/NIF bipolar electrolytic cells (1.55 V). The excellent electrocatalytic activity stems from the special electron transfer mechanism formed by Ce4+/Ce3+ that facilitates the charge transfer process. This work provides an effective surface engineering strategy to design high-efficiency bifunctional electrocatalysts for producing clean hydrogen. [ABSTRACT FROM AUTHOR]

The use of copper–metal–organic framework (Cu-MOF) as a versatile electrocatalyst signifies a transformative breakthrough with profound implications for sustainable energy and advanced analytical capabilities in the biodiesel industry. We present an economically efficient, Cu-MOF microneedle decorated nickel foam (NF)-based electrochemical sensor for detecting glycerol (Gly) in biodiesel and as an electrocatalyst for glycerol fuel cells. Herein, we utilized a simple and efficient solvothermal approach to synthesize Cu-MOF, then conducted a comprehensive analysis to study the material's morphological, structural, and functional groups using different material characterization techniques like transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transmission infrared spectroscopy (FTIR), etc. The Cu-MOF-modified NF electrocatalyst shows a remarkable current density of 690 mA/cm2, and the sensor exhibits exceptional selectivity, sensitivity, and a low limit of detection (LOD) of 0.172 μM. Cu-MOF/NF is highly selective over other interfering species (methanol, Na+, K+, Ca2+, Mg2+ cations, and phosphates) and in biodiesel samples with an outstanding recovery percentage of ∼101%. The microneedle structure of Cu-MOF plays a pivotal role in augmenting catalytic activity, providing increased surface area and providing active sites for electrochemical reactions. This is the first report on the utilization of Cu-MOF as bifunctional electrocatalysts, exploring their applications in glycerol fuel cells for sustainable energy generation as well as their role in electrochemical sensing for the accurate quantification of glycerol in biodiesel samples. [ABSTRACT FROM AUTHOR]

We have developed a chemosensor using calix[4]arene, which features a thiosemicarbazone binding/sensing unit and a naphthalene chromogenic group. Our objective was to understand the intricate binding affinity of these chemosensors towards a diverse range of anions and cations using UV–Visible, HNMR and IR spectroscopic techniques. We showed that this chemosensor can form complexes with Ag(I) or Cu (II) and to detect CN− or F− ions by deprotonation of thiosemicarbazone. To understand the behavior of these interactions, our analysis provides information on the interaction patterns between the receptors and the ions. The sulfur and imine nitrogen on the thiosemicarbazone substituent are vital sites of engagement for cation ions, as evidenced by the observed changes in IR. HNMR studies for interaction with anions indicate the involvement of the thiosemicarbazone hydrogens. Interactions taking place during complex formation with cations lead to changes in the color of the solution or solid complex, easy to follow by UV–Vis spectrocopy. Our study improves the understanding of molecular recognition of this chemosensor, highlighting its potential for ion- selective detection. [ABSTRACT FROM AUTHOR]

Solar-light-driven CO2 reduction CO to CH4 and C2H6 is a complex process involving multiple elementary reactions and energy barriers. Therefore, achieving high CH4 activity and selectivity remains a significant challenge. Here, we integrate bifunctional Cu2O and Cu-MOF (MOF = metal-organic framework) core–shell co-catalysts (Cu2O@Cu-MOF) with semiconductor TiO2. Experiments and theoretical calculations demonstrate that Cu2O (Cu+ facilitates charge separation) and Cu-MOF (Cu2+ improves the CO2 adsorption and activation) in the core–shell structure have a synergistic effect on photocatalytic CO2 reduction, reducing the formation barrier of the key intermediate ⋆COOH and ⋆CHO. The photocatalyst exhibits high CH4 yield (366.0 µmol·g−1·h−1), efficient electron transfer (3283 µmol·g−1·h−1) and hydrocarbon selectivity (95.5%), which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO2 reduction reaction. This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components. [ABSTRACT FROM AUTHOR]

Abstract The pursuit of efficient and durable bifunctional electrocatalysts for overall water splitting in acidic media is highly desirable, albeit challenging. SrIrO3 based perovskites are electrochemically active for oxygen evolution reaction (OER), however, their inert activities toward hydrogen evolution reaction (HER) severely restrict the practical implementation in overall water splitting. Herein, an Ir@SrIrO3 heterojunction is newly developed by a partial exsolution approach, ensuring strong metal‐support interaction for OER and HER. Notably, the Ir@SrIrO3‐175 electrocatalyst, prepared by annealing SrIrO3 in 5% H2 atmosphere at 175 °C, delivers ultralow overpotentials of 229 mV at 10 mA cm−2 for OER and 28 mV at 10 mA cm−2 for HER, surpassing most recently reported bifunctional electrocatalysts. Moreover, the water electrolyzer using the Ir@SrIrO3‐175 bifunctional electrocatalyst demonstrates the potential application prospect with high electrochemical performance and excellent durability in acidic environment. Theoretical calculations unveil that constructing Ir@SrIrO3 heterojunction regulates interfacial electronic redistribution, ultimately enabling low energy barriers for both OER and HER.

Future commercial energy conversion and storage requisitions may involve using two-dimensional (2D) materials that retain their structure and are feasible for water electrolysis. In this study, we advance in tuning the electronic arrangement of 2D materials like ZrTe 2 /graphene oxide for electrocatalytic energy conversions such as oxygen evolution reaction (OER) as well as hydrogen evolution reaction (HER). The fabricated materials characterize via X-rays diffraction analysis (XRD), Scanning electron microscopy (SEM), and Brunauer Emmett Teller (BET) adsorption-desorption isotherm to confirm their structure, shape, size and porosity. Subsequently, the fabricated nanocomposite employs for the electrochemical characterization, and the resultant composite shows a meager overpotential of 208 mV with a minimal Tafel slope of 31 mV/dec at a current density of the 10 mA/cm2 for the oxygen evolution process and represents the overpotential of 242 mV@-10 mA/cm2 for hydrogen evolution process. The fabricated ZrTe 2 /GO nanocomposite also shows the high stability of 40 h compared to the individual materials. This strategy provides a novel approach to designing tellurium-based nanomaterials for various applications. [Display omitted] • The ZrTe 2 /GO nanocomposite was fabricated facile hydrothermal strategy. • The generated material displayed a lower overpotential of 208 mV@10 mA/cm2. • The material also showed minimal Tafel value of 31 mV/dec for OER. • The material acquired an overpotential of 242 mV@ 10 mA/cm2 for HER. • The ZrTe 2 /GO nanocomposite exhibits exceptional stability for 40 h in case of OER. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are recognized as the core reaction processes in regenerative energy storage and conversion systems. The design of cost-effective and high-performance bifunctional ORR/OER electrocatalysts (ECs) is very important for their substantial commercialization. Herein, sponge-like Co3O4 nanoparticles anchored on carbon (Sp-Co3O4/C) are successfully fabricated by a facile two-step solvothermal strategy for ORR/OER in an alkaline electrolyte. The Sp-Co3O4/C EC exhibits promising bifunctional ORR/OER activity with ORR onset potential (Eonset = 0.88 V vs RHE), half-wave potential (E1/2 = 0.75 V), limiting current density (j = −6.60 mA cm–2), OER onset potential (Eonset = 1.26 V), and OER overpotential for 10% energy conversion (η10 = 0.38 V) in 0.1 M KOH. It demonstrates a significantly lower reversibility index (ΔE = Ej10 – E1/2 = 0.86 V), comparable to standard Pt/C and RuO2 ECs. The superior ORR/OER performances of Sp-Co3O4/C EC can be ascribed to the synergistic contribution of a high electrochemically active surface area (48.33 m2 g–1), BET surface area (131 m2 g–1), the rich interfacial structure of the crystal facets (111), (220), and (311), and the abundant oxygen vacancies in the sponge-like morphology. Besides the methanol tolerance, accelerated durability and chronoamperometric test established excellent durability and stability in the electrocatalytic operation. This work offers insight into the development of high-performance ORR/OER ECs. [ABSTRACT FROM AUTHOR]

The reaction rate bottleneck during interconversion between insulating S8 (S) and Li2S fundamentally leads to incomplete conversion and restricted lifespan of Li−S battery, especially under high S loading and lean electrolyte conditions. Herein, we demonstrate a new catalytic chemistry: soluble semiquinone, 2‐tertbutyl‐semianthraquinone lithium (Li+TBAQ⋅−), as both e‐/Li+ donor and acceptor for simultaneous S reduction and Li2S oxidation. The efficient activation of S and Li2S by Li+TBAQ⋅− in the initial discharging/charging state maximizes the amount of soluble lithium polysulfide, thereby substantially improve the rate of solid–liquid‐solid reaction by promoting long‐range electron transfer. With in situ Raman spectra and theoretical calculations, we reveal that the activation of S/Li2S is the rate‐limiting step for effective S utilization under high S loading and low E/S ratio. Beyond that, the S activation ratio is firstly proposed as an accurate indicator to quantitatively evaluate the reaction rate. As a result, the Li−S batteries with Li+TBAQ⋅− deliver superior cycling performance and over 5 times higher S utilization ratio at high S loading of 7.0 mg cm−2 and a current rate of 1 C compared to those without Li+TBAQ⋅−. We hope this study contributes to the fundamental understanding of S redox chemical and inspires the design of efficient catalysis for advanced Li−S batteries. [ABSTRACT FROM AUTHOR]

[Display omitted] Designing cost-effective and robust bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is highly desired in hydrogen production from overall water splitting, but still suffers great challenges due to the sluggish catalytic OER/HER kinetics. In this paper, a surface/defect engineering strategy is developed to synthesize three-dimensional (3D) carbon foam (CF)-supported unique hierarchical Co 3 O 4 nanowires@NiO nanosheets core–shell nanostructured catalyst (NiO@Co 3 O 4 /CF) with rich oxygen-vacancies as a novel bifunctional catalyst for alkaline water splitting electrolysis. Benefited from the synergy of the 3D hierarchical core–shell structure and rich oxygen vacancies, the as-obtained NiO@Co 3 O 4 /CF shows both excellent OER (η 200 = 325 mV, η 500 = 374 mV) and HER (η 10 = 104 mV) activities with low Tafel slopes (64.26 mV dec−1 for OER and 109.14 mV dec−1 for HER, respectively) and outstanding stability. A simple overall water splitting electrolysis cell assembled by this bifunctional NiO@Co 3 O 4 /CF as both OER and HER catalysts requires only a cell voltage of 1.53 V to obtain the current density of 10 mA cm−2 and displays a long-term stability. This work has successfully developed an approach for rational design and novel synthesis of metal oxide hybrids as bifunctional electrocatalysts with high activity and stability for overall water splitting. [ABSTRACT FROM AUTHOR]

CaTi 2 O 4 (OH) 2 :Eu3+, CaTiO 3 :Eu3+ and [CaTi 2 O 4 (OH) 2 –CaTiO 3 ]:Eu3+ were synthesized by a solvothermal method without the help of templates or surfactants. And their structures, luminescence properties, and photocatalytic properties were systematically studied. The RIR (reference intensity ratio) data of CaTi 2 O 4 (OH) 2 were first investigated via X-ray diffraction (XRD), thus the ratios of each phase in the (m%CaTi 2 O 4 (OH) 2 -n%CaTiO 3):3%Eu3+ biphasic mixture was determined. The bandgap value of CaTi 2 O 4 (OH) 2 :3%Eu3+ is 0.28 eV less than that of CaTiO 3 :3%Eu3+. The specific surface area of CaTi 2 O 4 (OH) 2 is 8.2 times larger than that of CaTiO 3. Compared with CaTiO 3 :Eu3+, the CaTi 2 O 4 (OH) 2 :Eu3+ showed stronger luminescence intensity. The Judd-Ofelt theory analysis show that the Eu3+ ions in CaTi 2 O 4 (OH) 2 :Eu3+ have low local symmetry, high Eu–O bonds covalence and low ligands electron density. The photocatalytic properties of CaTi 2 O 4 (OH) 2 :y%Eu3+, CaTiO 3 :x%Eu3+ and [62.2%CaTi 2 O 4 (OH) 2 -37.8%CaTiO 3 ]:3% Eu3+ were comparatively studied in detail. The band-gap value of [62.2 % CaTi 2 O 4 (OH) 2 –37.8%CaTiO 3 ]:3%Eu3+ is significantly reduced due to the presence of heterojunctions compared to CaTi 2 O 4 (OH) 2 :y%Eu3+ and CaTiO 3 : x%Eu3+. The built-in electric potential at heterojunction interface will guide electrons and holes to move in opposite directions, therefore [CaTi 2 O 4 (OH) 2 –CaTiO 3 ]:Eu3+ has excellent photocatalytic activity. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] Transition metal phosphides are highly efficient catalysts that do not rely on noble metals, which have shown great potential in replacing noble metal catalysts and contributing to the advancement of the electrocatalytic hydrogen production industry. To further enhance the catalytic performance of transition metal phosphides, researchers have discovered that cationic vacancy defects can be utilized to regulate their electronic structure, thereby improving their catalytic properties. In this research, we present the successful synthesis of a bifunctional Ni 2 P electrocatalyst (V Fe -Ni 2 P) with cationic vacancy defects through electrodeposition and acid etching techniques. The introduction of cationic vacancies after acid etching is confirmed by electron paramagnetic resonance (EPR) spectroscopy. The V Fe -Ni 2 P electrocatalyst demonstrates excellent catalytic performance in alkaline environments, achieving a current density of 10 mA∙cm−2 at an overpotential of 52 mV for the hydrogen evolution reaction (HER), and the same current density with an overpotential of 154 mV for the oxygen evolution reaction (OER). Additionally, the V Fe -Ni 2 P/NF electrode exhibits remarkable stability over 1000 cyclic voltammetric cycles for both HER and OER. This study presents a novel approach for the synthesis and performance control of highly-efficient transition metal phosphide electrocatalysts, which holds significant importance in the development and design of new energy materials. [ABSTRACT FROM AUTHOR]

Advancing green hydrogen production technologies relies heavily on the development of highly efficient and durable bifunctional catalysts for overall water splitting. Herein, this study reports the ruthenium‐modified hollow cubic molybdenum‐cobalt phosphide (Ru‐MoCoP) as exceptional performance electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Theoretical calculations and experimental results indicate that the incorporation of Ru not only serves as an efficient active site, but also adjusts the electronic structure and improves the reactivity of the original sites, as well as generates more phosphorus vacancies, which improves the electrical conductivity and exposes more active sites. Benefiting from the advantages triggered by the incorporation of Ru mentioned above, the Ru‐MoCoP delivers low overpotentials of 55 and 240 mV at 10 mA cm−2 for HER and OER, respectively. Furthermore, the electrolyzer assembled with Ru‐MoCoP achieves a current density of 50 mA cm−2 at 1.6 V and can be operated stably for 150 h. Notably, the assembled two‐electrode system can be powered by a single commercial AA battery, accompanied with evident gas bubble evolution. This research proposes a promising strategy for the development of highly efficient bifunctional phosphide catalysts, aiming to achieve efficient energy conversion in a wide range of industrial applications. [ABSTRACT FROM AUTHOR]

A promising step towards a carbon-free gas diffusion electrode (CF-GDE) design for alkaline applications is shown in this work. MnO x ´s are electrodeposited on nickel foam by varying the settings, and then they were annealed at 300 °C. These CF-GDEs were characterized and compared with a commercial carbon-based GDE (GDE ref). Samples were analyzed by XRD, SEM, X-ray tomography, contact angle method, nitrogen sorption, and electrochemical methods. Electrochemical impedance spectroscopy confirmed the higher reactant transport of CF-GDEs during OER and ORR. The large pore size of the CF-GDE substrate (nickel foam) results in a high supply of catalyst sites deep inside the CF-GDE. The transport distance of gaseous O 2 is also reduced since the thin electrolyte film is at the gas bulk of the CF-GDE. The catalytic bifunctionality was additionally examined by galvanostatic measurements at 5 and 10 mA cm− 2. A promising CF-GDE exhibited 0.43 V η OER and −2.43 V η ORR at 10 mA cm−2. Lastly, long-term stability measurements of 2100 cycles at 1.5 V (OER) and −0.75 V (ORR) vs. Hg/HgO in 1 M NaOH show the carbon corrosion of GDE ref (60% current density loss) and a stable current density of CF-GDE. • Designing a bifunctional carbon-free gas diffusion electrode (CF-GDE) for alkaline applications. • The CF-GDE indicated a higher reactant supply than the carbon-based GDE. • Higher OER activity due to large substrate pores of Ni foam combined with MnO x coating. • In situ formation of NiMn layered double hydroxides increased CF-GDEs current density. [ABSTRACT FROM AUTHOR]

Developing highly efficient bifunctional transition metal-based electrocatalysts is important for reducing the practical costs of water splitting. Herein, we present a flower-shaped disorderly nickel-iron nitride nanosheets bifunctional electrocatalysts (NiFeN x /NF), which was prepared in situ on a nickel foam substrate using a hydrothermal and thermal ammonia-reduction method. The unique structure of the flower-shaped disorderly nanosheets increases the amount of electrocatalytic active sites and promotes efficiency of both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) by facilitating charge and mass transfer. The bifunctional catalyst demonstrated exceptional performance with overpotentials of only 78 mV for HER and 280 mV for OER at current densities of 10 mA cm−2 and 100 mA cm−2, respectively. Additionally, the NiFeN x /NF exhibited outstanding stability, achieving a cell voltage of only 1.53 V for overall water splitting at 10 mA cm−2 in 1.0 M KOH, and continuously operated for 90 h at 20 mA cm−2 without significant voltage increase. These findings contribute to the development of high-performance, cost-effective, and environmentally friendly bifunctional catalysts based on transition metals for water splitting. • A disorderly flower-shaped NiFeN x nanosheets bifunctional electrocatalyst. • In-situ NiFeN x grown on nickel foam via hydrothermal and thermal ammonia-reduction. • NiFeN x /NF achieved an overall water splitting cell voltage of 1.53 V at 10 mA cm−2. [ABSTRACT FROM AUTHOR]

Base-pairing small RNAs and primary miRNAs encode small proteins and thus are denoted dual-function, bifunctional, or dual-component RNAs. Proteins encoded by these base-pairing RNAs generally are small [<50 amino acids (aa) in bacteria and <100 aa in eukaryotes] but perform a range of functions. It is likely that many more dual-function RNAs with important regulatory roles remain to be identified. RNAs are commonly categorized as being either protein-coding mRNAs or noncoding RNAs. However, an increasing number of transcripts, in organisms ranging from bacteria to humans, are being found to have both coding and noncoding functions. In some cases, the sequences encoding the protein and the regulatory RNA functions are separated, while in other cases the sequences overlap. The protein and RNA can regulate similar or distinct pathways. Here we describe examples illustrating how these dual-function (also denoted bifunctional or dual-component) RNAs are identified and their mechanisms of action and cellular roles. We also discuss the synergy or competition between coding and RNA activity and how these regulators evolved, as well as how more dual-function RNAs might be discovered and exploited. [ABSTRACT FROM AUTHOR]

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers.

Current environmental challenges and the shrinking fossil‐fuel feedstock are important criteria for the next generation of polymer materials. In this context, we present a fully bio‐based material, which shows promise as a thermoplastic elastomer (TPE). Due to the use of β‐farnesene and L‐lactide as monomers, bio‐based feedstocks, namely sugar cane and corn, can be used. A bifunctional initiator for the carbanionic polymerization was employed, to permit an efficient synthesis of ABA‐type block structures. In addition, the "green" solvent MTBE (methyl tert‐butyl ether) was used for the anionic polymerisation, enabling excellent solubility of the bifunctional anionic initiator. This afforded low dispersity (Đ=1.07 to 1.10) and telechelic polyfarnesene macroinitiators. These were employed for lactide polymerization to obtain H‐shaped triblock copolymers. TEM and SAXS revealed clearly phase‐separated morphologies, and tensile tests demonstrated elastic mechanical properties. The materials featured two glass transition temperatures, at ‐ 66 °C and 51 °C as well as gyroid or cylindrical morphologies, resulting in soft elastic materials at room temperature. [ABSTRACT FROM AUTHOR]

One of the efficient approaches to achieving net-zero greenhouse gas emissions is the 100% atom-economical conversion of the greenhouse gas carbon dioxide (CO2) to cost-effective, less toxic cyclic carbonates that can act as green solvents and abundant C1 synthon in organic synthesis. In this work, we have synthesized an Indium Metal–Organic Framework (MOF), functionalized with triazole MIL-68(In)-NHTr (Tr = 1-methylene-1,2,4-triazole) as a bifunctional catalyst for the synthesis of cyclic carbonates from epoxides with high yield (96%) and selectivity (100%) under solvent-free ambient reaction conditions (CO2 pressure 1 bar, temperature 50 °C, and reaction time 6 h). The synergistic acid–base effect of Indium SBU and the triazole of MIL-68(In)-NHTr make this a better catalyst than the conventional MIL-68(In)-NH2. This new catalyst was non-leachable and was reusable for six consecutive catalytic cycles without appreciable loss in the catalytic efficiency and crystallinity of the MOF framework. [ABSTRACT FROM AUTHOR]

Propargylic alcohols are readily available bifunctional (alkyne and hydroxyl groups) synthons, which recognize as one of the attractive synthetic feedstock in organic transformations. Especially, in recent years the employment of these valuable molecules has frequently been observed in the literature. Hence, the present review highlights recent advancements in the application of propargylic alcohols in the cyclization, substitution, and addition reactions. [ABSTRACT FROM AUTHOR]