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The interplay between constituent localized and itinerant electrons of metal clusters defines their physical and chemical properties. In turn, the electronic and geometrical structures are strongly entwined and exhibit strong size-dependent variations. Current understanding of low-energy excited states of metal clusters relies on stand-alone theoretical investigations and few comparisons with measured properties, since direct identification of low-lying states is lacking hitherto. Here, we report on the measurement of low-lying electronic transitions in cationic cobalt clusters using infrared photofragmentation spectroscopy. Broad and size-dependent absorption features were observed within 0.056 – 0.446 eV, well above the energies of the sharp absorption bands caused by cluster vibrations. Complementary time-dependent density functional theory calculations reproduce the main observed absorption features, providing direct evidence that they correspond to transitions between electronic states of mainly d-character, arising from the open d-shells of the Co atoms and the high spin multiplicity of the clusters. Large classes of metal clusters are expected to have dipole-allowed electronic transitions in the near-infrared, but precise experimental characterization of such low-lying states is lacking. Here, the authors probe cationic cobalt clusters of 4 to 15 atoms using IR photofragmentation spectroscopy with krypton as a messenger atom to show that low-lying electronic excited states are responsible for the size-dependent radiative decay of these highly excited clusters. [ABSTRACT FROM AUTHOR]

Niobium carbide MXenes belong to a class of metal carbide MXenes with niobium as the early transition metal. The transformation of niobium carbide MXene sheets in to few-layer MXene sheets, the combination of the niobium-based MXene with other materials, delamination, intercalation, and partial oxidation of the niobium carbide MXene sheets have resulted in the formation of a material with excellent energy storage and sensing potentials. Herein, the synthesis and classification of the niobium-based MXenes (NBM), their application as sensing materials for a wide range of analytes, and their energy storage potentials are discussed exhaustively. The various transformations of niobium carbide MXenes over the last two decades are also established in this timely review. Essentially, this review is a searchlight on the prospects of NBM, the current state of their application, and their relevance in the materials research community. [ABSTRACT FROM AUTHOR]

The intriguing chemistry of chalcogen (S, Se)-containing ligands and their capability to bridge multiple metal centres have resulted in a plethora of reports on transition metal complexes featuring hydrosulfide (HS-) and polychalcogenides (En2-, E = S, Se). While a large number of such molecules are strictly organometallic complexes, examples of non-organometallic complexes featuring HS- and En2- with N-/O-donor ligands are relatively rare. The general synthetic procedure for the transition metal-hydrosulfido complexes involves the reaction of the corresponding metal salts with HS-/H2S and this is prone to generate sulfido bridged oligomers in the absence of sterically demanding ligands. On the other hand, the synthetic methods for the preparation of transition metal-polychalcogenido complexes include the reaction of the corresponding metal salts with En2- or the two electron oxidation of low-valent metals with elemental chalcogen, often at an elevated temperature and/or for a long time. Recently, we have developed new synthetic methods for the preparation of two new classes of binuclear transition metal complexes featuring either HS-, or Sn2- and Sen2- ligands. The new method for the synthesis of transition metal-hydrosulfido complexes involved transition metal-mediated hydrolysis of thiolates at room temperature (RT), while the method for the synthesis of transition metal-polychalcogenido complexes involved redox reaction of coordinated thiolates and exogenous elemental chalcogens at RT. An overview of the synthetic aspects, structural properties and intriguing reactivity of these two new classes of transition metal complexes is presented. [ABSTRACT FROM AUTHOR]

In this work, we introduced a simple aggregation-induced emission enhancement (AIEE) sensor (PHCS) which can selectively detect and discriminate three environmentally and biologically imperative heavy metal ions (Cu2+, Co2+ and Hg2+) and a hazard class 1 categorized nitro-explosive picric acid (PA) in differential media. By virtue of its weak fluorescence attributes in pure organic medium owing to the synergistic operation of multiple photophysical quenching mechanisms, the molecular probe showcased highly selective 'TURN ON' fluorogenic response towards hazardous Hg2+ with a limit of detection (LOD) as low as 97 nM. Comprehensive investigation of binding mechanism throws light on the cumulative effect of probe-metal complexation induced chelation enhanced fluorescence (CHEF) effect and subsequent AIEE activation within the formed probe-metal adducts. Noteworthily, the probe (PHCS) can be readily used in real water samples for the quantitative determination of Hg2+ in a wide concentration range. In addition, the probe displayed modest colorimetric recognition performances to selectively detect and discriminate two essential heavy metal ions (Cu2+ and Co2+) with a LOD of 96 nM and 65 nM for Cu2+ and Co2+ respectively, in semi-aqueous medium. Intriguingly, based on high photoluminescence efficiency, the AIEE active nano-aggregated PHCS displayed a remarkable propensity to be used as a selective and ultra-sensitive 'TURN-OFF' fluorogenic chemosensor towards PA with LOD of 34.4 ppb in aqueous medium. Finally, we specifically shed light on the interaction of PHCS hydrosol towards PA using some unprecedented techniques, which helped uncover new photophysical insights of probe-explosive molecule interaction. We shed light on novel photophysical insights toward unique multifunctional sensory aptitude of a simple aggregation-induced emission enhancement active organic functional molecule in differential media, enabling ultra-sensitive discriminative detection of toxic heavy metal ions and explosive molecule simultaneously. [ABSTRACT FROM AUTHOR]

Reaction of [CuH(PPh3)]6 with 1 equiv. of Tl(OTf) results in formation of [Cu6TlH6(PPh3)6][OTf] ([1]OTf]), which can be isolated in good yields. Variable‐temperature 1H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl−H orbital interaction. According to DFT, the 1H chemical shift of the Tl‐adjacent hydride ligands of [1]+ includes 7.7 ppm of deshielding due to spin‐orbit effects from the heavy Tl atom. This study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl−H interaction. [ABSTRACT FROM AUTHOR]

[Display omitted] Transition metal chalcogenides (TMCs) hold great potential for sodium-ion batteries (SIBs) owing to their multielectron conversion reactions, yet face challenges of poor intrinsic conductivity, sluggish diffusion kinetics, severe phase transitions, and structural collapse during cycling. Herein, a self-templating strategy is proposed for the synthesis of a class of metal cobalt-doped NiSe nanoparticles confined within three-dimensional (3D) N -doped macroporous carbon matrix nanohybrids (Co-NiSe/NMC). The cation defect engineering within the developed Co-NiSe and 3D N -doped carbon plays a crucial role in enhancing intrinsic conductivity, reinforcing structural stability, and reducing the barrier to sodium ion diffusion, which are verified by a series of electrochemical kinetic analyses and density functional theory calculations. Significantly, such cation defect engineering not only reduces overpotential but also accelerates conversion reaction kinetics, ensuring both exceptional high-rate capability and extended durability. Consequently, the optimally engineered Co-NiSe/NMC demonstrates a remarkable rate performance, delivering 390 mAh g−1 at 10 A g−1. Moreover, it exhibits an unprecedented lifespan, maintaining a remarkable capacity of 403 mAh g−1 after 1400 cycles and 318 mAh g−1 after 4000 cycles, even at high rates of 1.0 and 2.0 A g−1, respectively. This work marks a substantial advancement in achieving both high performance and prolonged cycle life in sodium-ion batteries. [ABSTRACT FROM AUTHOR]

Molecular diodes are of considerable interest for the increasing technical demands of device miniaturization. However, the molecular diode performance remains contact‐limited, which represents a major challenge for the advancement of rectification ratio and conductance. Here, it is demonstrated that high‐quality ultrathin organic semiconductors can be grown on several classes of metal substrates via solution‐shearing epitaxy, with a well‐controlled number of layers and monolayer single crystal over 1 mm. The crystals are atomically smooth and pinhole‐free, providing a native interface for high‐performance monolayer molecular diodes. As a result, the monolayer molecular diodes show record‐high rectification ratio up to 5 × 108, ideality factor close to unity, aggressive unit conductance over 103 S cm−2, ultrahigh breakdown electric field, excellent electrical stability, and well‐defined contact interface. Large‐area monolayer molecular diode arrays with 100% yield and excellent uniformity in the diode metrics are further fabricated. These results suggest that monolayer molecular crystals have great potential to build reliable, high‐performance molecular diodes and deeply understand their intrinsic electronic behavior. [ABSTRACT FROM AUTHOR]

High-entropy alloys (HEAs) are a class of metal alloys consisting of four or more molar equal or near-equal elements. HEA nanomaterials have garnered significant interest due to their wide range of applications, such as electrocatalysis, welding, and brazing. Their unique multi-principle high-entropy effect allows for the tailoring of the alloy composition to facilitate specific electrochemical reactions. This study focuses on the synthesis of high-purity HEA nanoparticles using the method of femtosecond laser ablation synthesis in liquid. The use of ultrashort energy pulses in femtosecond lasers enables uniform ablation of materials at significantly lower power levels compared to longer pulse or continuous pulse lasers. We investigate how various femtosecond laser parameters affect the morphology, phase, and other characteristics of the synthesized nanoparticles. An innovative aspect of our solution is its ability to rapidly generate multi-component nanoparticles with a high fidelity as the input multi-component target material at a significant yielding rate. Our research thus focuses on a novel synthesis of high-entropy alloying CuCoMn1.75NiFe0.25 nanoparticles. We explore the characterization and unique properties of the nanoparticles and consider their electrocatalytic applications, including high power density aluminum air batteries, as well as their efficacy in the oxygen reduction reaction (ORR). Additionally, we report a unique nanowire fabrication phenomenon achieved through nanojoining. The findings from this study shed light on the potential of femtosecond laser ablation synthesis in liquid (FLASiL) as a promising technique for producing high-purity HEA nanoparticles. [ABSTRACT FROM AUTHOR]

A new class of homoleptic metal(II) complexes of general formula [M(L1–4)2]2Cl in which L1=1‐([1,1′‐biphenyl]‐4‐yl)‐N‐(2‐((‐pyridin‐2‐ylmethylene)amino)ethyl)methanimine, L2=1‐([1,1′‐biphenyl]‐4‐yl)‐N‐(2‐((‐pyridin‐2‐ylmethylene)amino)phenyl)methanimine, L3=1‐([1,1′‐biphenyl]‐4‐yl)‐N‐(2‐((‐pyridin‐2‐ylmethylene)amino)‐4‐nitrophenyl)methanimine and L4=4‐(([1,1′‐biphenyl]‐4‐ylmethylene)amino)‐3‐((−pyridin‐2‐ylmethylene)amino)benzophenone, and M=Ni(II) (1–4), Cu(II) (5–8) and Zn(II) (9–12) have been synthesized and characterized. The IR spectra reveal the involvement of azomethine and 2‐formylpyridine ring nitrogen atoms in chelation. The UV‐Vis and EPR spectral studies envisage distorted octahedral geometry around metal(II) ion. All the complexes were stable for 72 h in biologically relevant solutions, and copper(II) complexes were reduced to Cu+ center in the presence of ascorbic acid solution. The binding studies of complexes with calf thymus DNA (CT‐DNA) indicate groove mode of binding, and the complexes 3, 7 and 11 containing the 4‐nitrophenyl substituent exhibit the highest binding affinity than the other complexes. Furthermore, the spectral studies also revealed the interaction of complexes with BSA through static mechanism. In vitro cytotoxicity activity of the complexes was screened against human lung adenocarcinoma (A549) and breast adenocarcinoma (MCF‐7) cancerous, and normal murine fibrosarcoma (L929) cell lines. The molecular docking studies of the homoleptic metal(II) complexes show hydrophobic, π–π, σ–π and hydrogen bonding interactions with EGFR/VEGFR2 kinase receptors. [ABSTRACT FROM AUTHOR]

Zeolitic imidazolate framework (ZIF) is a new class of metal organic framework (MOF) with imidazolate ligands as linkers and metal ions as metal centers. A bismuth zeolitic imidazolate framework (Bi-ZIF) was prepared by laser ablation in liquid environment as a physical bottom-up method for the first time. The samples were characterized by Fourier transform infrared (FTIR) spectroscopy for evaluation of functional groups, X-ray diffraction (XRD) for determination of crystal structure, field emission scanning electron microscope (FESEM), and transmission electron microscope (TEM) for investigation of morphology and size of produced nanostructures. The antibacterial activity of samples was investigated by Escherichia coli (E. coli) as gram-negative bacterium and Staphylococcus aureus (S. aureus) as gram-positive bacterium. Based on the results, laser ablation is a quick, capable, clean, and simple candidate method for synthesizing different kinds of ZIF. [ABSTRACT FROM AUTHOR]

Ether‐based electrolytes have good compatibility for lithium metal, which is widely used in lithium metal batteries (LMBs). However, the electrolyte is not suitable for high voltage (>4.0 V) due to its poor anti‐oxidation behavior. Herein, an anion chemistry strategy is designed for a typical 1,2‐dimethoxyethane (DME)‐based electrolyte with 1 m lithium bis(fluorosulfonyl)imide (LiFSI), by using nitrate anion (NO3−) with a high donor number (DN) value to regulate the coordination of DME and FSI–. It is evidenced that the interaction between them is weakened due to the competitive advantage of NO3−, therefore a weakly solvating electrolyte is achieved. It promotes the formation of an inorganic‐rich passivation layer on the cathode and facilitates the de‐solvation process, thus it is suitable for high voltage even at 4.5 V. The anion‐regulated weakly solvating electrolyte (ARWSE) designed here is different from the high‐concentration electrolyte (HCE), localized HCE, and WSE which are of high cost and complexity. The ARWSE is demonstrated to be an adjustable electrolyte system, effectively improving the interfacial chemistry of LMBs. [ABSTRACT FROM AUTHOR]

Photodynamic therapy (PDT) has garnered significant attention in the fields of cancer treatment and drug-resistant bacteria eradication due to its non-invasive nature and spatiotemporal controllability. Iridium complexes have captivated researchers owing to their tunable structure, exceptional optical properties, and substantial Stokes displacement. However, most of these complexes suffer from aggregation-induced quenching, leading to diminished luminous efficiency. In contrast to conventional photosensitizers, photosensitizers exhibiting aggregation-induced luminescence (AIE) properties retain the ability to generate a large number of reactive oxygen species when aggregated. To overcome these limitations, we designed and synthesized a novel iridium complex named Ir-TPA in this study. It incorporates quinoline triphenylamine cyclomethylated ligands that confer AIE characteristics for Ir-TPA. We systematically investigated the photophysical properties, AIE behavior, spectral features, and reactive oxygen generation capacity of Ir-TPA. The results demonstrate that Ir-TPA exhibits excellent optical properties with pronounced AIE phenomenon and robust capability for producing singlet oxygen species. This work not only introduces a new class of metal iridium complex photosensitizer with AIE attributes but also holds promise for achieving remarkable photodynamic therapeutic effects in future cellular experiments and biological studies. [ABSTRACT FROM AUTHOR]

This study focuses on the utilization of two‐dimensional Ti3C2 MXene as a catalyst for photocatalytic hydrogen production. MXenes, a class of transition metal carbides/nitrides, exhibit exceptional properties conducive to enhancing photocatalytic reactions. This research explores the performance of Ti3C2 MXene as a cocatalyst in photocatalytic systems, aiming to improve charge separation, inhibit recombination, and facilitate efficient hydrogen evolution from water under light irradiation. The synthesis methods, catalyst‐loading strategies, and overall photocatalytic mechanisms are investigated, shedding light on the potential of Ti3C2 MXene as a promising material for advancing hydrogen production through sustainable means. [ABSTRACT FROM AUTHOR]

Wire arc additive manufacturing (WAAM) is a class of arc-based metal additive manufacturing (AM) under the category of direct energy deposition. As compared to other metal-based AM techniques, WAAM is capable of fabricating medium-to-large sized part (having low level of design complexity) with near fully-dense structure. Ease of near-net shaping with high material utilization rate has made the process economic in various industrial applications staring from prototype to customized product fabrication. Quality of the built part is strongly affected by the feedstock wire composition, welding parameters and deposition strategy. Due to complicated thermal history, WAAMed part suffers from considerable anisotropy in microstructure as well as mechanical properties. The present work attempts to fabricate a 3D slab by layer-wise deposition of molten SS308L-T1 feedstock wire through CMT + MIG based WAAM process. Initially, a few pilot experiments (by depositing single track bead-on-plate welds and stacked weld specimens) are performed to determine values of the appropriate process parameters for WAAM of SS308L part. The appropriate setting of parameters which includes current, voltage, gas flow rate, nozzle-to-plate distance, start/end current percentage, degree of overlap and deposition strategy (applicable for stacked specimens), etc. are obtained based on visual inspection of the built quality and measurable features of bead geometry. Finally, a 3D wall is successfully fabricated having approximate dimension 150 × 25 × 30 mm3. The microstructure evolution and mechanical property characterization of the as built part are carried out. It is experienced that microstructure and mechanical property of WAAMed SS308L are location-dependent. The as built microstructure contains δ ferrite (skeletal, vermicular and lathy morphologies) which is deposited at grain boundaries of γ austenite. The middle zone of the fabricated slab appears to be relatively softer than top and bottom zones; middle zone corresponds to the lowest tensile strength along horizontal direction (~ 541 MPa) but the highest fracture strain (elongation percent ~ 38%). The average tensile strength along horizontal direction is obtained as ~ 548 MPa. Fractographic results of failed tensile specimens evidence ductile fracture mode characterized by dimples along with the presence of second-phase spherical particles. The average microhardness of the as built SS308L obtained is 171 HV0.1. [ABSTRACT FROM AUTHOR]

The new class of Tricarboxylate-Bismuth (TB)-based Metal Organic Frameworks (MOFs) was attempted, using the impressive capability of alkaline earth metal Bismuth (Bi), to realize more massive complex structures for real-world applications including supercapacitors, energy storage devices, biomedical imaging, drug delivery, fluorescence sensing and far-UVC applications. The grown structure and band gap of the TB-based MOFs samples were characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy, and Ultraviolet-Visible Absorption Spectroscopy (UV-Vis spectra), respectively. The SEM observation identifies the TB-based MOFs nanosheet layered with orthorhombic structure, which shows strong agglomeration with a grain size of 668 nm. The EDS analysis indicates the presence of Bi-peaks as well as carbon peaks (organic linkers) in the grown samples. Furthermore, the peak of TB-based MOFs structure during the Raman spectroscopy was also confirmed. The optical band gap of the newly synthesized TB-based MOFs was estimated and the optical band gap ( E g) approximately ∼ 5. 4 5 eV was confirmed. These findings open the possibility of Bi-based MOFs for the applications in far-UVC emission range. [ABSTRACT FROM AUTHOR]

Magnéli phases are an important class of transition metal oxides widely utilized in fields such as batteries, electrocatalysis, and photocatalysis. However, there are no reports on the use of Magnéli phases as additives in ceramic sintering. In order to explore the impact of the Magnéli phase as an additive on the sintering process, self-made Magnéli phase Ti 4 O 7 powder was added to the graded mixture of titanium dioxide (TiO 2) coarse powder and nanopowder, and sintered under atmospheric conditions in this study. The sintering characteristics, microstructure, and mechanical properties of TiO 2 ceramics with different content of Ti 4 O 7 were characterized. The results revealed that the addition of Ti 4 O 7 contributed to the reduction of the densification temperature of TiO 2 ceramics. Compared to the undoped sample, the addition of 1 wt% Ti 4 O 7 powder significantly improved the flexural strength and Vickers hardness of TiO 2 ceramics by 13.5% and 24.8%. According to the results of thermal analysis, UV–Vis–NIR, and XPS, the mechanism of Ti 4 O 7 in the sintering process of TiO 2 ceramics under atmospheric conditions was systematically discussed. This work not only obtained TiO 2 ceramics with improved performance but also showed the tremendous potential of Magnéli phases in the field of ceramic sintering. [ABSTRACT FROM AUTHOR]

Herein, we used first-principles calculations and the particle swarm optimization technique to predict a highly incompressible W0.5Al0.5N phase with the space group R 3 ¯ m (166). Our results reveal that this phase, which was characterized by a negative formation enthalpy, is thermodynamically and dynamically stable, as revealed by the absence of imaginary modes in the phonon spectra. Furthermore, its energetic stability at a pressure of 15 GPa indicates a feasible strategy for experimental synthesis. The high performance stems from the optimized octahedral coordination between N and W/Al. Additionally, the good elastic parameters with BH of 310 GPa, GH of 206 GPa, and HV of 27 GPa confirm that it has preferable mechanical behaviors among the various W0.5Al0.5N phases and is even superior to those of the experimentally well-established NaCl-type phase. Based on the recently developed strain–stress method, it is shown that the ideal indentation strength of R 3 ¯ m (166) is about 32.7 GPa in the (1 1 ¯ 0) [0 0 1] direction, which is in excellent agreement with estimated HV. Therefore, our findings open the possibility for producing a new class of transition metal aluminum nitrides that have a broad range of applications. [ABSTRACT FROM AUTHOR]

The aim of this study is to develop a novel class of hybrid metal matrix composite materials (HMMCs) using the ultrasonic-assisted stir casting method with varying weight percentages of zirconium diboride (1, 3, 5wt%) and two weight percentages of fly ash. X-ray diffraction (XRD) and EDAX are used to confirm the fabrication of proposed HMMCs. A scanning electron microscope (SEM) is used to see the distribution of ZrB2 and fly ash particles throughout the matrix. The mechanical properties like tensile strength and hardness of the composites were investigated. A linear reciprocating dry sliding wear test at temperatures 25 °C, 75 °C, 125 °C, and 175 °C is performed on a multi-tribometer. A Taguchi-based grey relational analysis is used to optimize the input parameters to analyse the wear properties of HMMCs. The grey relational analysis shows that five weight percentages of ZrB2 and two weight percentages of fly ash are the optimum input parameters for the lowest specific wear rate. Hardness is improved by 53.33%, and ultimate tensile strength (UTS) is enhanced by 23% for the inclusion of 5 weight percentages of zirconium diboride with 2% fly ash compared to AA7075 alloy. Tribological property like wear resistance is also enhanced with the increasing weight percentage of zirconium diboride. [ABSTRACT FROM AUTHOR]

Design, synthesis, and in vitro antitumor properties of Cu(I) and Ag(I) phosphane complexes supported by the anions of sterically hindered β-diketone ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) featuring trifluoromethyl or methyl groups on the phenyl moieties have been reported. In order to compare the biological effects of substituents on the phenyl moieties, the analogous copper(I) and silver(I) complexes of the anion of the parent 1,3-diphenylpropane-1,3-dione (HLPh) ligand were also synthesized and included in the study. In the syntheses of the Cu(I) and Ag(I) complexes, the phosphane coligands triphenylphosphine (PPh3) and 1,3,5-triaza-7-phosphaadamantane (PTA) were used to stabilize silver and copper in the +1 oxidation state, preventing the metal ion reduction to Ag(0) or oxidation to Cu(II), respectively. X-ray crystal structures of HLCF3 and the metal adducts [Cu(LCF3)(PPh3)2] and [Ag(LPh)(PPh3)2] are also presented. The antitumor properties of both classes of metal complexes were evaluated against a series of human tumor cell lines derived from different solid tumors, by means of both 2D and 3D cell viability studies. They display noteworthy antitumor properties and are more potent than cisplatin in inhibiting cancer cell growth. [ABSTRACT FROM AUTHOR]

Sequence-encoded biomolecules such as DNA and peptides are powerful programmable building blocks for nanomaterials. This paradigm is enabled by decades of prior research into how nucleic acid and amino acid sequences dictate biomolecular interactions. The properties of biomolecular materials can be significantly expanded with non-natural interactions, including metal ion coordination of nucleic acids and amino acids. However, these approaches present design challenges because it is often not well-understood how biomolecular sequence dictates such non-natural interactions. This Feature Article presents a case study in overcoming challenges in biomolecular materials with emerging approaches in data mining and machine learning for chemical design. We review progress in this area for a specific class of DNA-templated metal nanomaterials with complex sequence-to-property relationships: DNA-stabilized silver nanoclusters (AgN–DNAs) with bright, sequence-tuned fluorescence colors and promise for biophotonics applications. A brief overview of machine learning concepts is presented, and high-throughput experimental synthesis and characterization of AgN–DNAs are discussed. Then, recent progress in machine learning-guided design of DNA sequences that select for specific AgN–DNA fluorescence properties is reviewed. We conclude with emerging opportunities in machine learning-guided design and discovery of AgN–DNAs and other sequence-encoded biomolecular nanomaterials. [ABSTRACT FROM AUTHOR]

Seagrasses provide crucial ecosystem services in the coastal environment, but are under increasing threat associated with anthropogenic activities. Seagrass meadows effectively trap suspended sediment, a key vector for trace metal transport, by altering local hydrodynamic conditions around their leaves and stems. As a result, seagrass meadows often have different geochemical sediment characteristics compared to adjacent bare sediments and may accumulate higher concentrations of trace metals. The aim of this systematic review was to identify research trends and knowledge gaps in the relationships between metals and seagrasses. The systematic search of the literature identified a total of 191 relevant articles. Although seagrasses have a broad geographic distribution, the highest diversity and endemism exists in the Indo-Pacific region, yet most studies (40%) were conducted in the Mediterranean Sea. There were also taxonomic gaps with some common species groups, including Amphibolis and Thalassodendron spp., being poorly studied. The reviewed studies examined the relationship between seagrass and 39 metal elements. There were no studies examining rare-earth elements (REEs) or platinum-group elements (PGEs), both of which are critical classes of metals in emerging technologies. Furthermore, the review determined that all 191 studies focused on the impact of metals on seagrasses, while only six also considered the effect of seagrasses on metal geochemistry in sediments. We conclude that further research is necessary to address these key gaps in knowledge to better understand the role(s) of seagrasses in the distribution, immobilization, and release of trace metals in coastal ecosystems. [ABSTRACT FROM AUTHOR]

Azoheteroarenes are emerging classes of photoswitches with versatile scaffolds that offer distinct features such as efficient photoisomerization, tunable stability of the photoswitched states, and bidirectional photoswitching. Moreover, the heteroatoms of such photoswitches exhibit coordination ability to bind to the metal centers. The resulting azoheteroarene‐based metal complexes can be designed and developed to tune various metal‐based properties towards intriguing applications such as in optics, magnetic properties, data storage applications, and catalysis. Despite the diverse utility of azopyridines in such contexts, other azoheteroarenes, particularly the state‐of‐the‐art five‐membered heterocycle‐based photoswitches, remain under‐explored. In this Review, we describe the diverse classes of azoheteroarene‐coordinated metal complexes reported in the literature and survey their photoswitching behaviour and applications. Furthermore, we identify potential azoheteroarene candidates for building photochrome‐coupled metal complexes and supramolecular architectures for maximizing the photo‐tuning of metal‐related properties. [ABSTRACT FROM AUTHOR]

WC–Co cemented carbides build one of the important classes of metal matrix composites. We show in this paper that the use of machine vision methods makes it possible to obtain sufficiently informative statistical data on the topology of the interfaces between tungsten carbide grains (WC) and a cobalt matrix (Co). For the first time, the outlines of the regions of the cobalt binder were chosen as a tool for describing the structure of cemented carbides. Numerical processing of micrographs of cross sections of three WC–Co alloys, which differ in the average grain size, was carried out. The distribution density of the angles in the contours of cobalt "lakes" is bimodal. The peaks close to 110° (so-called outcoming angles) correspond to the contacts between the cobalt binder and the WC/WC grain boundaries. The peaks close to 240° (or incoming angles) correspond to the WC "capes" contacting the cobalt "lakes" and are determined by the angles between facets of WC crystallites. The distribution density of the linear dimensions of the regions of the cobalt binder, approximated with ellipses, were also obtained. The distribution density exponentially decreases with the lengths of the semi-axes of the ellipsoid, approximating the area of the cobalt binder. The possible connection between the obtained data on the shape of cobalt areas and the crack trajectories in cemented carbides is discussed. [ABSTRACT FROM AUTHOR]

Metal complexes feature a wide range of available geometries, diversified lability, controllable hydrolytic stability, and easily available rich redox activity. These characteristics, combined with the specific properties of coordinated organic molecules, result in many different mechanisms of biological action, making each of the myriads of the classes of metal coordination compounds unique. This focused review presents combined and systematized results of the studies of a group of copper(I) (pseudo)halide complexes with aromatic diimines and tris(aminomethyl)phosphines of a general formula [CuX(NN)PR3], where X = I− or NCS−, NN = 2,2′-bipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline or 2,2′-biquinoline, and PR3 = air-stable tris(aminomethyl)phosphines. The structural and electronic properties of the phosphine ligands and luminescent complexes are discussed. The complexes with 2,9-dimethyl-1,10-phenanthroline, apart from being air- and water-stable, exhibit a very high in vitro antimicrobial activity against the Staphylococcus aureus and Candida albicans. Moreover, some of these complexes also show a strong in vitro antitumor activity against human ovarian carcinoma cell lines: MDAH 2774 and SCOV 3, CT26 (mouse colon carcinoma), and A549 (human lung adenocarcinoma) cell lines. The tested complexes are moderately able to induce DNA lesions through free radical processes, however the trends do not reflect observed differences in biological activity. [ABSTRACT FROM AUTHOR]

In modern era, wireless communications at ultrafast speed are need of the hour and search for its solution through cutting edge sciences is a new perspective. To address this issue, the data rates in order of terabits per second (TBPS) could be a key step for the realization of emerging sixth generation (6G) networks utilizing terahertz (THz) frequency regime. In this context, new class of transition metal dichalcogenides (TMDs) have been introduced as potential candidates for future generation wireless THz technology. Herein, a strategy has been adopted to synthesize high-quality monolayer of molybdenum di-sulfide (MoS2) using indigenously developed atmospheric pressure chemical vapor deposition (APCVD) set-up. Further, the time-domain transmission and sheet conductivity were studied as well as a plausible mechanism of terahertz response for monolayer MoS2 has been proposed and compared with bulk MoS2. Hence, the obtained results set a stepping stone to employ the monolayer MoS2 as potential quantum materials benefitting the next generation terahertz communication devices. [ABSTRACT FROM AUTHOR]

Advancements in modern medicine have improved the quality of life across the globe and increased the average lifespan of our population by multiple decades. Current estimates predict by 2030, 12% of the global population will reach a geriatric age and live another 3–4 decades. This swelling geriatric population will place critical stress on healthcare infrastructures due to accompanying increases in age-related diseases and comorbidities. While much research focused on long-lived individuals seeks to answer questions regarding how to age healthier, there is a deficit in research investigating what aspects of our lives accelerate or exacerbate aging. In particular, heavy metals are recognized as a significant threat to human health with links to a plethora of age-related diseases, and have widespread human exposures from occupational, medical, or environmental settings. We believe heavy metals ought to be classified as a class of gerontogens (i.e., chemicals that accelerate biological aging in cells and tissues). Gerontogens may be best studied through their effects on the "Hallmarks of Aging", nine physiological hallmarks demonstrated to occur in aged cells, tissues, and bodies. Evidence suggests that cellular senescence—a permanent growth arrest in cells—is one of the most pertinent hallmarks of aging and is a useful indicator of aging in tissues. Here, we discuss the roles of heavy metals in brain aging. We briefly discuss brain aging in general, then expand upon observations for heavy metals contributing to age-related neurodegenerative disorders. We particularly emphasize the roles and observations of cellular senescence in neurodegenerative diseases. Finally, we discuss the observations for heavy metals inducing cellular senescence. The glaring lack of knowledge about gerontogens and gerontogenic mechanisms necessitates greater research in the field, especially in the context of the global aging crisis. [ABSTRACT FROM AUTHOR]

To improve the catalytic activity of 3d transition metal catalysts, redox‐active ligands are a promising tool. These ligands influence the oxidation state of the metal center as well as the ground spin‐state and make the experimental determination of both properties challenging. Therefore, first‐principles calculations, in particular employing density functional theory with a proper choice of exchange‐correlation (xc) functional, are crucial. Common xc functionals were tested on a simple class of metal complexes: homoleptic, octahedral tris(diimine) iron(II) complexes. The spin‐state energy splittings for most of these complexes showed the expected linear dependence on the amount of exact exchange included in the xc functionals. Even though varying redox‐activity affects the electronic structure of the complexes considerably, the sensitivity of the spin‐state energetics to the exact exchange admixture is surprisingly small. For iron(II) complexes with highly redox‐active ligands and for a broad range of ligands in the reduced tris(diimine) iron(I) complexes, self‐consistent field convergence to local minima was observed, which differ from the global minimum in the redox state of the ligand. This may also result in convergence to a molecular structure that corresponds to an energetically higher‐lying local minimum. One criterion to detect such behavior is a change in the sign of the slope for the dependence of the spin‐state energy splittings on the amount of exact exchange. We discuss possible protocols for dealing with such artifacts in cases in which a large number of calculations makes checking by hand unfeasible. [ABSTRACT FROM AUTHOR]

A rare example of a structurally characterized metal quinoline complex was prepared using a non-covalent quinoline-based proteasome inhibitor (Quin1), and a related complex bearing an inactive quinoline ligand (Quin2) was also synthesized. The quinolines are prepared by a one-pot procedure involving titanium-catalyzed alkyne iminoamination and are bound to ruthenium by reaction with CpRu(NCMe)3+ PF6− in CH2Cl2. The arene of the quinoline is η6-bonded to the ruthenium metal center. The kinetics of quinoline displacement were investigated, and reactivity with deuterated solvents follows the order acetonitrile > DMSO > water. Quinolines with more methyl groups on the arene are more kinetically stable, and RuCp(Quin1)+ PF6− (1), which has two methyl groups on the arene, is stable for days in DMSO. In contrast, a very similar complex (2) made with Quin2 having no methyl groups on the arene was readily displaced by DMSO. Both 1 and 2 are stable in 9 : 1 water/DMSO for days with no measurable displacement of the quinoline. The cytotoxicity of the quinolines, their CpRu+-complexes, and CpRu(DMSO)3+ PF6− was investigated towards two multiple myeloma cell lines: MC/CAR and RPMI 8226. To determine whether the activity of the complexes was related to the nature of the quinoline ligands, two structurally similar quinoline ligands with vastly different biological properties were investigated. Quin1 is a cytotoxic proteasome inhibitor, whereas Quin2 is not a proteasome inhibitor and showed no discernable cytotoxicity. The ruthenium complexes showed poor cellular proteasome inhibition. However, both 1 and 2 showed good cytotoxicity towards RPMI 8226 and MC/CAR, with 1 being slightly more cytotoxic. For example, 1 has a CC50 = 2 μM in RPMI 8226, and 2 has a CC50 = 5 μM for the same cell line. In contrast, CpRu(DMSO)3+ PF6− was quite active towards MC/CAR with CC50 = 2.8 μM but showed no discernible cytotoxicity toward RPMI 8226. The mechanism of action responsible for the observed cytotoxicity is not known, but the new Ru(Cp)(Quin)+ PF6− complexes do not cross-link DNA as found for platinum-based drugs. It is concluded that the Ru(Cp)(Quin)+ PF6− complexes remain intact in the cellular assays and constitute a new class of cytotoxic metal complexes. [ABSTRACT FROM AUTHOR]

Adding nucleating agents has been a successful strategy to boost the heat resistance of poly(L-lactic acid) (PLLA) by increasing the crystallinity. In this study, a new series of bio-based complexes as nucleating agents for PLLA, including twelve combinations of three eco-friendly metal ions (Zn, Mg, Ca) and four biomass-derived α-hydroxy acids, were successfully synthesized to respectively investigate the effects of metal ions as well as ligands on nucleation capacity of complexes. By investigating the non-isothermal and isothermal crystallization at 135 °C of PLLA with 0.3 wt% loading of complexes, both zinc and magnesium salts of L-mandelic acid showed excellent nucleation capacities. And magnesium L-mandelate performed better, raising the crystallinity of PLLA to 44.4 % as well as minimizing its crystallization half-time from 73 min to 2.7 min. The growth and denser distribution of PLLA spherulites on the salt surface were also observed by POM, reflecting epitaxial nucleation as the possible mechanism. A novel inspiration, utilizing VESTA software to simulate the crystal structure of zinc L-mandelate (Zn(L-MA) 2), was proposed to determine the nucleation mechanism. Also, using polyethylene terephthalate (PET) as a test protocol, the rationality of the model could be approved by checking the fitness of nucleating prediction and experiment results. [Display omitted] • Biomass-derived ligands and non-toxic metal ions synthesized as a class of PLLA efficient nucleating agents. • The nucleation ability and nucleation mechanism of nucleating agents was studied. • A novel strategy using computer simulation was developed to successfully explain the nucleation mechanism. • It has a good nucleation effect on other polyester, such as PET. [ABSTRACT FROM AUTHOR]

Materials science and technology, with the advent of nanotechnology, has brought about innumerable nanomaterials and multi-functional materials, with intriguing yet profound properties, into the scientific realm. Even a minor functionalization of a nanomaterial brings about vast changes in its properties that could be potentially utilized in various applications, particularly for biological applications, as one of the primary needs at present is for point-of-care devices that can provide swifter, accurate, reliable, and reproducible results for the detection of various physiological conditions, or as elements that could increase the resolution of current bio-imaging procedures. In this regard, iron oxide nanoparticles, a major class of metal oxide nanoparticles, have been sweepingly synthesized, characterized, and studied for their essential properties; there are 14 polymorphs that have been reported so far in the literature. With such a background, this review's primary focus is the discussion of the different synthesis methods along with their structural, optical, magnetic, rheological and phase transformation properties. Subsequently, the review has been extrapolated to summarize the effective use of these nanoparticles as contrast agents in bio-imaging, therapeutic agents making use of its immune-toxicity and subsequent usage in hyperthermia for the treatment of cancer, electron transfer agents in copious electrochemical based enzymatic or non-enzymatic biosensors and bactericidal coatings over biomaterials to reduce the biofilm formation significantly. [ABSTRACT FROM AUTHOR]

Metal borohydride (MBH4) compounds have been studied thoroughly for their potential as hydrogen storage materials. Zirconium borohydrides are one such class of metal borohydrides with hydrogen storage potential, however the interaction between the hydrides from BH4− and Zr presents an intriguing feature worth exploring. Cp2Zr(BH4)2 has been investigated for its potential as a hydrogen storage material and as a precursor for other hydrogen storage materials. But, to our knowledge, the structure of Cp2Zr(BH4)2 showing the position of the hydrides is unknown. We present here the crystal structure and DFT calculations of Cp2Zr(BH4)2 showing, for the first time, the position of the hydrides in relation to Zr. The crystal structure and DFT calculations of Cp2Zr(BH4)2 is reported showing, for the first time, the position of the hydrides attached to boron [ABSTRACT FROM AUTHOR]

Rare earth oxides (REOs) and metals as an important class of materials have generated global interest in modern technology. Here, eight REOs (R 2 O 3 , R = Yb, Er, Sm, Eu, Y, Gd, Dy, and Ce) are identified those are mostly used in diverse chemical and industrial sectors. In this concise review the applications of these REOs in corrosion protection, thermal barrier coating, hydrophobic coating, catalytic reactions, refrigeration, photoactivity, environmental, and tribological sector are briefly summarized, which are sparsely documented in the existing literature review. In what follows, recently published relevant literature is systematically evaluated and key insights are addressed. The use of REOs as nonstoichiometric compounds or as doping agents to enhance the system performance of specific applications is commendable. Related lab-scale studies, therefore, will invoke the potential exploitation of individual or blended REOs for large-scale commercialization. However, phase transformation and high energy consumption in the thermal coating, multi-step fabrication of hydrophobic coating, the building of aromatic pollutants in catalysis, magnetic entropy shift in refrigeration, and photo corrosion are some of the inherent hindrances of these oxides. These issues warrant prompt actions from the scientific community to deliver cost-effective, efficient, and environmentally sustainable applications. Regardless, this review is expected to provide critical insights into REOs for contrasting industrial applications and encourage interested researchers to dig deeper in finding the best strategic solutions to counter prevalent challenges. [Display omitted] • Catalysis: REOs enhanced photocatalytic dye degradation activity. • Tribological: REOs enhance wear properties of hybrid composites. • Coating: REOs are potential for thermal barrier & corrosion-resistance coating. • Sustainability: REOs' contribution to recycling materials and water treatment. • Prospect: REOs possess great potential in eco-friendly applications. [ABSTRACT FROM AUTHOR]

Transparent conducting materials (TCMs) are essential components for a variety of optoelectronic devices, such as photovoltaics, displays and touch screens. In recent years, extensive efforts have been made to develop TCMs with both high electrical conductivity and optical transmittance. Based on material types, they can be mainly categorized into the following classes: metal oxides, metal nanowire networks, carbon-material-based TCMs (graphene and carbon nanotube networks) and conjugated conductive polymers (PEDOT:PSS). This review will discuss the fundamental electrical and optical properties, typical fabrication methods and the applications in solar cells for each class of TCMs and highlight the current challenges and potential future research directions. [ABSTRACT FROM AUTHOR]

35889296 11 Ni Z.H., Lv H.J., Yang G.Y. Recent Advances of Ti/Zr-Substituted Polyoxometalates: From Structural Diversity to Functional Applications. Guo-Yu Yang et al. [[5]] synthesized three new transition metal-substituted POM compounds. Polyoxometalates are a special class of soluble metal oxides (intermediate state) between monomeric metal oxides and infinite metal oxides, which have amazing differences in sizes, chemical compositions, and physical properties from monomeric and infinite metal oxides. All the previously reported Ge-V-O compounds were totally based on aliphatic organic ligands; compounds B 1 b and B 2 b are the first examples of Ge-V-O clusters containing aromatic organic ligands. [Extracted from the article]

High entropy alloys are a promising new class of metal alloys with outstanding radiation resistance and thermal stability. The interaction with hydrogen might, however, have desired (H storage) or undesired effects, such as hydrogen-induced embrittlement or tritium retention in the fusion reactor wall. High entropy alloy WMoTaNbV and bulk W samples were used to study the quantity of irradiation-induced trapping sites and properties of D retention by employing thermal desorption spectrometry, secondary ion mass spectrometry, and elastic recoil detection analysis. The D implantation was not found to create additional hydrogen traps in WMoTaNbV as it does in W, while 90 at% of implanted D is retained in WMoTaNbV, in contrast to 35 at% in W. Implantation created damage predicted by SRIM is 0.24 dpa in WMoTaNbV, calculated with a density of 6.044 × 10 22 atoms/cm 3 . The depth of the maximum damage was 90 nm. An effective trapping energy for D in WMoTaNbV was found to be about 1.7 eV, and the D emission temperature was close to 700 °C. [ABSTRACT FROM AUTHOR]

Additive manufacturing (AM) has transformed the way of manufacturing metallic parts due to its ability of rapid prototyping, customization, reduced waste, and cost-effectiveness for small-batch manufacturing, and it has been increasingly replacing milling and molding processes. Directed energy deposition and powder-based fusion AM are the major classes of metal AM technologies, which are already well-established to print high-volume and small complex parts, respectively. However, the increasing demand for the fabrication of small devices, due to the miniaturization trend that is occurring in several industries fields, requires the development of specialized metal AM systems with the ability to increase the resolution of the printed parts. Thus, micro-metal additive manufacturing (MMAM) systems are now being developed using a scaling-down approach of the currently well-established metal AM technologies. In this review, a state-of-art analysis of the existing body of knowledge including the existing MMAM technologies, process parameters, and main results associated with MMAM was compiled and critically discussed. A surface texture index is defined, and a comparison of the trade-off between surface finishing and the building rate was performed considering the metal AM processes and the already developed scaled-down technologies. Additionally, other important aspects of the process (e.g., cost-related, health, environmental risks) are discussed. [ABSTRACT FROM AUTHOR]

The main challenges and obstacles to the development of hydrogen/carbon monoxide production from the splitting of water/carbon dioxide through two-step solar thermochemical cycles are strongly related to material concerns. Ineed, ceria is the main benchmark redox material used in such processes because it provides very good oxidation reaction kinetics, reactions reversibility and thermal cycling stability. This is at the expense of a low reduction yield (non-stoichiometry δ in CeO2-δ) at relatively high temperatures (≥1400 °C), which requires operation at low oxygen partial pressures during the reduction step. Hence, the specific fuel output per mass of redox material, i.e., the amount of H2/CO produced per cycle, remains low, thereby limiting the overall solar-to-fuel conversion efficiency. Perovskites offer larger amounts of fuel produced per cycle but the reaction kinetics are slow. This study addresses the thermochemical investigation of a new class of metal oxides, namely high entropy oxides (HEOs), with the aim of improving the specific amount of fuel generated per cycle with good kinetic rates. Different formulations of high entropy oxides were investigated and compared using thermogravimetric analysis to evaluate their redox activity and ability to split CO2 during thermochemical cycles. Among the different formulations tested, five HEOs yielded CO with a maximum specific fuel output of 154 µmol/g per cycle. These materials' performances exceeded the production yields of ceria under similar conditions but are still far from the production yields reached with lanthanum–manganese perovskites. This new class of materials, however, opens a wide path for research into new formulations of redox-active catalysts comparing favorably with the ceria redox performance for solar thermochemical synthetic fuel production. [ABSTRACT FROM AUTHOR]

Sluggish sulfur reduction reaction (SRR) kinetics remains a formidable challenge in Li–S electrochemistry. In this sense, the rational design of single‐atom species has become a burgeoning practice to expedite sulfur redox, where the underlying catalytic mechanism otherwise remains elusive. Herein, a class of metal single‐atom modified porous carbon nanofiber films (MSA PCNFs, M = Fe, Co, or Ni), fabricated via a generic synthetic strategy, as mediators to boost SRR kinetics is reported. Throughout electrokinetic measurement and operando instrumental probing, NiSA PCNF is evidenced to harness the catalytic superiority toward the rate‐determining step (i.e., liquid–solid conversion) of the SRR process. Density functional theory (DFT) simulations further reveal that the catalytic features of M–N–C moieties in catalyzing the Li2S precipitation rely heavily upon the coordination environments of adjacent carbon atoms and d‐orbital configurations of metal centers. In response, the thus‐derived S/NiSA PCNF cathode realizes an encouraging areal capacity of 14.12 mAh cm−2 under elevated sulfur loading (10.2 mg cm−2) and lean electrolyte usage (E/S ratio ≈ 5.5 μL mg−1). This work offers insight into the identification of exact catalytic moieties for different transition metal M–N–C single‐atom SRR mediators, showcasing a meaningful guidance and potential impact on Li–S catalysis. [ABSTRACT FROM AUTHOR]

Water microbial purification is one of the hottest topics that threats human morbidity and mortality. It is indispensable to purify water using antimicrobial agents combined with several technologies and systems. Herein, we introduce a class of nanosized metal organic framework; Zeolitic imidazolate framework (ZIF-67) cages encapsulated with polyoxometalates synthesized via facile one-step co-precipitation method. We employed two types of polyoxometalates bioactive agents; phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) that act as novel antibacterial purification agents. Several characterization techniques were utilized to investigate the morphological, structural, chemical, and physical properties such as FESEM, EDS, FTIR, XRD, and N2 adsorption/desorption isotherms techniques. The antibacterial assessment was evaluated using colony forming unit (CFU) against both Escherichia coli and Staphylococcus aureus as models of Gram-negative and Gram-positive bacteria, respectively. The PTA@ZIF-67 showed higher microbial inhibition against both Gram-positive and Gram-negative bacteria by 98.8% and 84.6%, respectively. Furthermore, computational modeling using density functional theory was conducted to evaluate the antibacterial efficacy of PTA when compared to PMA. The computational and experimental findings demonstrate that the fabricated POM@ZIF-67 materials exhibited outstanding bactericidal effect against both Gram-negative and Gram-positive bacteria and effectively purify contaminated water. [ABSTRACT FROM AUTHOR]

A new hybrid perovskite of [FCH2CH2NH3][Mn(HCOO)3] has been successfully prepared by utilizing the ammonium of FCH2CH2NH3+, and it is the first example incorporating F‐substituted ammonium in the class of ammonium metal formate framework. The compound crystallizes in polar, orthorhombic space group Pna21, and the cell parameters are a=8.5901(3)–8.7158(6), b=8.4613(3)–8.5216(6), c=12.4837(4)–12.6106(9) Å and V=907.36(5)–936.6(1) Å3 from 80 K up to 410 K just before the decomposition, showing positive thermal expansions in all directions and no structural phase transition in the temperature region. The FCH2CH2NH3+ cation in the cavity of the NaCl‐like Mn‐formate framework adopts N−C−C−F gauche conformation, and its NH3+ and F ends are anchored to the anionic framework by N−H⋅⋅⋅O and C−H⋅⋅⋅F H‐bonds. The large dislocation of the NH3+ end from the anionic framework, about 1.4 Å, results in an estimated high electric polarization about 10 μCcm−2 for the polar structure. The material is also a spin‐canted antiferromagnet with the Néel temperature of 8.3 K. [ABSTRACT FROM AUTHOR]

Liquid metals are a class of materials with a millennia‐long history, albeit until 200 years ago, mostly centered on mercury‐based applications. The knowledge of mercury's toxicity and the discovery of it's bioaccumulation and biomagnification in the late 20th century resulted in phasing out mercury for copious application. Lead‐based, bismuth‐based, and sodium‐based technology has partially replaced mercury, but due to toxicity or reactivity issues, replacements for lead and sodium are sought. The discovery of indium and, especially, gallium has allowed for the third generation of alloys with a melting point close to room temperature. This review gives a comprehensive overview of the technological developments of fusible and liquid metals, i. e. metals and alloys with melting points below ca. 250 °C, from the early days to current research and industrial application. Special emphasis is focused on important steppingstones and recent developments of gallium‐based alloys as well as how they could be used for future applications. [ABSTRACT FROM AUTHOR]

• Simple and affordable co-precipitation method for creating a potent and robust bifunctional electrocatalyst. • In situ , superficial oxidation studies have been conducted on the OER and HER processes. • Synthesized electrocatalyst has more active sites, which aids in the redox of FeII/III and CuI/II. • The Fe 8 Cu 2 CN/NF// Fe 8 Cu 2 CN/NF exhibits ultra-durability (over 180 h) with a negligible loss of 5.4 %. • During water electrolysis, 6.55 mmol h−1cm−2 of hydrogen was produced. Hydrogen generation by water electrolysis is considered a clean, green, and renewable approach for sustainable energy demands and environmental management. The efficient use of earth-abundant transition metal catalysts is cost-effective and limits the usage of noble metal catalysts like IrO 2 , RuO 2 , and Pt/C. The PBAs (Prussian Blue Analogs) are a class of transition metal hexacyanoferrates that can be tailored for specific electrochemical reactions. Both iron and copper are well-proven transition metals for catalytic activities owing to their aptitude to achieve much-pronounced reactant transformations under minor circumstances, as well as their environmental friendliness, cyclability, and long-term durability at 10 mA cm−2 in 1.0 M KOH, the greenly synthesized Fe 8 Cu 2 CN (PBAs) on NF (Nickel foam) displays a low overpotential of 150 mV (118 mV dec−1) for HER (Hydrogen Evolution Reaction) and 290 mV (112 mV dec−1) for OER (Oxygen Evolution Reaction). Fe 8 Cu 2 CN displays ultra-stable behavior (150 h) with a slight current loss of 4.2 % for OER and 3.4 % for HER, respectively. The interaction of Fe, Cu, and CN (cyanide) enhances the rate of reaction kinetics. The designing of a water electrolyzer that delivers 10 mA cm−2 at 1.60 V is made possible with the help of the improved bifunctional catalyst Fe 8 Cu 2 CN/NF. The Fe 8 Cu 2 CN/NF//Fe 8 Cu 2 CN/NF exhibits long-last durability (over 180 h) with a negligible current reduction of 5.4 %. The improved effectiveness of the synthesized catalyst is demonstrated by the solar water splitting at 1.66 V. These findings suggest that Fe 8 Cu 2 CN/NF//Fe 8 Cu 2 CN/NF can be used to produce large quantities of H 2 at very affordable prices. [Display omitted] [ABSTRACT FROM AUTHOR]

We design a series of transition metal phthalocyanine molecules (TM@C24H12N6, TM = Ti, V, Mn, etc.) as electrocatalysts for NRR. Our results indicates that Tc@C24H12N6 is the promising electrocatalyst with good adsorption, activation, low onset potential and high selectivity. [Display omitted] • A series of TM-phthalocyanine molecules (TM@C 24 H 12 N 6 , TM = Ti, V, Mn,Fe, Co, Ni, Zr, Nb, Mo, Tc, Ru, Rh, Pd, W, and Re) for NRR are investigated. • The onset potentials are −0.50, −0.43, and −0.65 V respectively for Nb/Mo/Tc@C 24 H 12 N 6. • Tc@C 24 H 12 N 6 exhibits high selectivity for NRR and a Faraday efficiency (FE) of 99.9 %. In this manuscript, we design a class of transition metal subphthalocyanine molecules as electrocatalysts for NRR. The results indicate that the Nb, Mo, and Tc systems can effectively absorb and activate a N 2 molecule and reduce onset potentials (−0.50, −0.43, and −0.65 V, respectively). Among them, the Tc@C 24 H 12 N 6 molecule has exceptionally high selectivity for NRR with the Faraday efficiency (FE) of ∼ 99.9 %. Therefore, the good stability, outstanding adsorption and activation properties of N 2 , very low onset potential, and high selectivity of Tc@C 24 H 12 N 6 indicate it possesses promising catalytic activity for NRR among the investigated catalysts. [ABSTRACT FROM AUTHOR]