High-selective separation recovery of Ni, Co, and Mn from the spent LIBs via acid dissolution and multistage oxidation precipitation.

For recovering Ni, Co, and Mn from lithium-ion batteries, traditional chemical precipitation methods demonstrate low selectivity and significantly contribute to environmental pollution. This study proposes a separation recovery technique for transition metals, specifically Ni, Co, and Mn, from spent LIBs, involving "acid dissolution" and "multistage oxidation precipitation". More than 98% of transition metals can be extracted from spent LIBs using a low acid concentration (0.5 M) without reducing agents. The feasibility of separating different metals via multistage oxidation precipitation, based on their different electrode potentials for oxidizing Me2+ (Me = Mn/Co/Ni), was confirmed. The combination of oxidizing agent S2O82- and the precipitant OH- was universally applied to the fractional precipitation of Mn, Co, and Ni respectively. About 99% of Mn, 97.06% Co, and 96.62% Ni could be precipitated sequentially by changing the concentrations of S2O82- and the pH value of solution. XRD, XPS, XRF, ICP-MS and other methods were employed to elucidate the mechanism behind the multistage oxidation precipitation of target metal compounds, exploiting the differential electrode potentials for oxidizing Me2+ ions. This technique surpasses traditional solvent extraction in cost-effectiveness and selectivity, showing promise for large-scale industrial applications in recovering Mn, Co, and Ni.

Chameleonic Cages: Encapsulation of Anionic, Neutral, and Cationic Guest Species within [Fe4L4]8+ Tetrahedral Cages Synthesised from the tris(4-aminophenyl)phosphate pro-Ligand.

An adaptable Fe(II) tetrahedral cage, [Fe4L4][BF4]8 (L = tris(4-(((E)-pyridin-2-ylmethylene)amino)phenyl) phosphate), has been synthesised via self-assembly. By modulating the orientation of its pendant P=O groups, the cage was found to be capable of encapsulating anionic, neutral, and cationic guests, which was confirmed in the solid state via single-crystal X-ray diffraction (SCXRD) and in solution by high-resolution mass spectroscopy (HR-MS), as well as by NMR (1H, 19F, 31P) studies where possible.

Tuning transition metals layered-electroplated on bimetallic MxCu1-x crystallites (M = Fe, Co, Ni, and Zn) to boost ammonia yield in electrocatalytic reduction of nitrate wastewaters.

Nitrate-containing wastewaters have been recognized as an important source for recovering valuable ammonia. This work targets integrating a series of transition metals (M = Fe, Co, Ni, and Zn) onto Cu crystallites through a layered-plating method. The strategy to promote the nitrate reduction reaction (NO3-RR) involves tuning M surfaces in specific ratios for the hydrogenation of nitrogenous species on MxCu1-x electrodes. Electrochemical analysis and operando Raman spectra identified that a solid-state Cu2O-to-Cu0 transition acted as the primary mediator, while its high corrosion resistance protected the M metals or metal oxides from inactivation in nitrate-to-ammonia pathways. Among bimetals, FeCu was the best combination, with the order of performance in constant potential electrolysis, Fe0.36Cu0.64 > Ni0.73Cu0.27 > Co0.34Cu0.66 > Zn0.64Cu0.36. The collaboration of Cu and M in deoxygenating nitrate and subsequently hydrogenating NOx at respective overpotentials is key to enhancing ammonia yield. Nitrate removal (96 %), NH3 selectivity (93 %), and Faradaic efficiency (92 %) were optimized on Fe0.36Cu0.64 electrode at -0.6 V (vs. RHE). A steady yield as high as 14,080 µg h-1 mg-1 was achieved at 30 mA cm-2 using a real water sample (NO3- ∼ 500 mg-N L-1, pH 4) as the input stream, continuously operated for 96 h.

2-Aminoacetophenone formation through UV-C induced degradation of tryptophan in the presence of riboflavin in model wine: Role of oxygen and transition metals.

2-Aminoacetophenone is an off-flavor that can result from tryptophan degradation via riboflavin-photosensitized reaction. This study investigates the impact of light exposure, provided by a UV-C source, oxygen concentrations and transition metals on the formation of 2-aminoacetophenone in model wine containing tryptophan and riboflavin. Irrespective of oxygen and transition metals, >85% of tryptophan were degraded via first-order kinetics to unknown product(s). However, longer light exposure and more oxygen caused 2-aminoacetophenone concentrations to increase. Transition metals decelerated the 2-aminoacetophenone formation and acetaldehyde was formed suggesting photo-Fenton reaction occurred as a competitive reaction. The degradation rate of riboflavin inclined with less oxygen and in the presence of transition metals due to the depletion of oxygen by photo-Fenton reaction. Oxygen plays an important role in the regeneration of riboflavin and therefore must be seen as an intensifier for light-induced 2-aminoacetophenone formation. This paper provides new insights into riboflavin-photosensitized reactions.

Unveiling Anti-malarial, Antimicrobial, Antioxidant Efficiency and Molecular Docking Study of Synthesized Transition Metal Complexes Derived From Heterocyclic Schiff Base Ligands.

Malaria, a persistent and ancient adversary, continues to impact vast regions worldwide, afflicting millions and severely affecting human health and well-being. Recently, despite significant progress in combating this parasitic disease, malaria remains a major global health concern, especially in areas with limited resources and vulnerable populations. Consequently, identifying and developing effective agents to combat malaria and its associated dysfunctions is essential therefore the two new Schiff base ligands incorporated Co(II), Ni(II), Cu(II) and Zn(II) ions were synthesized and thoroughly characterized. The synthesized compounds were assessed for in vitro anti-malarial and antimicrobial efficacy, compounds (9, 10) demonstrated highest potential with IC50=1.08±0.09 to 1.18±0.04 µM against P. falciparum and MIC=0.0058 µmol/mL against C. albicans and E. coli, respectively. The complexes (5, 6) were effectively reduce mitigate oxidative stress with lowest IC50 value of 2.69±0.12 to 2.87±0.09 µM. Moreover, the biological findings were reinforced by a molecular docking investigation involving the potential compounds (2, 7-10) against dihydroorotate dehydrogenase and sterol 14-alpha demethylase proteins which exposed complex's excellent biological response than their parent ligands. ADMET profiling was used to confirm the compounds' oral drug-like features. This research offers promising prospects for future multi-functional drug innovations targeting malaria, pathogenic infections, and oxidative stress.

Metabolic Derangement of Essential Transition Metals and Potential Antioxidant Therapies.

Essential transition metals have key roles in oxygen transport, neurotransmitter synthesis, nucleic acid repair, cellular structure maintenance and stability, oxidative phosphorylation, and metabolism. The balance between metal deficiency and excess is typically ensured by several extracellular and intracellular mechanisms involved in uptake, distribution, and excretion. However, provoked by either intrinsic or extrinsic factors, excess iron, zinc, copper, or manganese can lead to cellular damage upon chronic or acute exposure, frequently attributed to oxidative stress. Intracellularly, mitochondria are the organelles that require the tightest control concerning reactive oxygen species production, which inevitably leaves them to be one of the most vulnerable targets of metal toxicity. Current therapies to counteract metal overload are focused on chelators, which often cause secondary effects decreasing patients' quality of life. New therapeutic options based on synthetic or natural antioxidants have proven positive effects against metal intoxication. In this review, we briefly address the cellular metabolism of transition metals, consequences of their overload, and current therapies, followed by their potential role in inducing oxidative stress and remedies thereof.

Enzymatic CO2 reduction catalyzed by natural and artificial Metalloenzymes.

The continuously increasing level of atmospheric CO2 in the atmosphere has led to global warming. Converting CO2 into other carbon compounds could mitigate its atmospheric levels and produce valuable products, as CO2 also serves as a plentiful and inexpensive carbon feedstock. However, the inert nature of CO2 poses a major challenge for its reduction. To meet the challenge, nature has evolved metalloenzymes using transition metal ions like Fe, Ni, Mo, and W, as well as electron-transfer partners for their functions. Mimicking these enzymes, artificial metalloenzymes (ArMs) have been designed using alternative protein scaffolds and various metallocofactors like Ni, Co, Re, Rh, and FeS clusters. Both the catalytic efficiency and the scope of CO2-reduction product of these ArMs have been improved over the past decade. This review first focuses on the natural metalloenzymes that directly reduce CO2 by discussing their structures and active sites, as well as the proposed reaction mechanisms. It then introduces the common strategies for electrochemical, photochemical, or photoelectrochemical utilization of these native enzymes for CO2 reduction and highlights the most recent advancements from the past five years. We also summarize principles of protein design for bio-inspired ArMs, comparing them with native enzymatic systems and outlining challenges and opportunities in enzymatic CO2 reduction.

Co(II) Macrocyclic Complexes with Amide-Glycinate Pendants as ParaCEST and Liposomal CEST Agents.

Macrocyclic Co(II) complexes with appended amide-glycinate groups were prepared to develop paramagnetic Co(II) chemical exchange saturation transfer (CEST) agents of reduced overall charge. Complexes with reduced charge and lowered osmolarity are important for their loading into liposomes and to provide complexes that are highly water soluble and well tolerated in animals. Co(L1) has two non-coordinating benzyl groups and two amide-glycinate pendants, whereas Co(L2) has two unsubstituted amide pendants and two amide-glycinate pendants on cyclam (1,4,8,11-tetraazacyclododecane). The 1H NMR spectrum of Co(L1) is consistent with a single cis-pendant isomer with both amide protons in the trans-configuration, as supported by an X-ray crystal structure. Co(L2) has a mixture of different isomers in solution, including the trans-1,4 and 1,8 pendant isomers. The Z-spectrum of Co(L1) shows one highly-shifted CEST peak, whereas Co(L2) exhibits six CEST peaks. Encapsulation of 40 mM Co(L1) in a liposome with osmotically-induced shrinking at 300 mOsm/L produces a liposomal CEST agent with saturation frequency offset of 3 ppm. Addition of the amphiphilic 1,4,7-triazacyclononane-based complex Co(L5) to the liposomal bilayer at 18 mM with Co(L1) encapsulated in the liposome at 50 mM changes the sign and increases the magnitude of the saturation frequency offset to -7.5 ppm at 300 mOsm/L.

Magnetic properties of CrMnGen (n = 3-20) clusters.

Due to the potential applications in next-generation micro/nano electronic devices and functional materials, magnetic germanium (Ge)-based clusters are receiving increasing attention. In this work, we reported the structures, electronic and magnetic properties of CrMnGen with sizes n = 3-20. Transition metals (TMs) of Cr and Mn tend to stay together and be surrounded by Ge atoms. Small sized clusters with n ≤ 8 prefer to adopt bipyramid-based structures as the motifs with the excess Ge atoms absorbed on the surface. Starting from n = 9, the structure with one TM atom interior appears and persists until n = 16, and for larger sizes n = 17-20, the two TM atoms are full-encapsulated by Ge atoms to form endohedral structures. The Hirshfeld population analyses show that Cr atom always acts as the electron donor, while Mn atom is always the acceptor except for sizes 3 and 6. The average binding energies of these clusters increase with cluster size n, sharing a very similar trend as that of CrMnSin (n = 4-20) clusters, which indicates that it is favorable to form large-sized clusters. CrMnGen (n = 6, 13, 16, 19, and 20) clusters prefer to exhibit ferromagnetic Cr-Mn coupling, while the remaining clusters are ferrimagnetic.

Metal-Flavonoid Interactions-From Simple Complexes to Advanced Systems.

For many years, metal-flavonoid complexes have been widely studied as a part of drug discovery programs, but in the last decade their importance in materials science has increased significantly. A deeper understanding of the role of metal ions and flavonoids in constructing simple complexes and more advanced hybrid networks will facilitate the assembly of materials with tailored architecture and functionality. In this Review, we highlight the most essential data on metal-flavonoid systems, presenting a promising alternative in the design of hybrid inorganic-organic materials. We focus mainly on systems containing CuII/I and FeIII/II ions, which are necessary in natural and industrial catalysis. We discuss two kinds of interactions that typically ensure the formation of metal-flavonoid systems, namely coordination and redox reactions. Our intention is to cover the fundamentals of metal-flavonoid systems to show how this knowledge has been already transferred from small molecules to complex materials.

Transition-Metal-Catalyzed Transformations for the Synthesis of Marine Drugs.

Transition metal catalysis has contributed to the discovery of novel methodologies and the preparation of natural products, as well as new chances to increase the chemical space in drug discovery programs. In the case of marine drugs, this strategy has been used to achieve selective, sustainable and efficient transformations, which cannot be obtained otherwise. In this perspective, we aim to showcase how a variety of transition metals have provided fruitful couplings in a wide variety of marine drug-like scaffolds over the past few years, by accelerating the production of these valuable molecules.

Anti-cancer property and DNA binding interaction of first row transition metal complexes: A decade update.

Metal ions carry out a wide variety of functions, including acid-base/redox catalysis, structural functions, signaling, and electron transport. Understanding the interactions of transition metal complexes with biomacromolecules is essential for biology, medicinal chemistry, and the production of synthetic metalloenzymes. After the coincidental discovery of cisplatin, importance of the metal complexes in biochemistry became a top priority for inquiry. In this review, a decade update on various synthetic strategies to first row transition metal complex and their interaction with DNA through non-covalent binding are explored. Moreover, this effort provides an excellent analysis on the efficacy of theoretical and practical approaches to the systematic generation of new non-platinum based metallodrugs for anti-cancer therapeutics.

Self-assembly of four Ni16 Molecular Wheels with Capsule and Tubular Supramolecular Architectures.

Four new Ni16 molecular wheels with the general formula [L4Ni16(RCOO)16(H2O)x(MeOH)12-x] (where H4L = 1,4-bis((E)-((2'-hydroxybenzyl)imino)methyl)-2,3-naphthalenediol, and R = H or Me) have been isolated and structurally characterised. Complexes C1 - C3 (R = Me)were formed using nickel(II) acetate and presented as polymorphs with the same formulation of charged components. The same wheel-like architecture was observed in C4 (R = H), which was prepared using nickel(II) formate, demonstrating the potential for further versatility of the system. In contrast to similar four-fold symmetric Ni(II) wheel clusters, measurements of the static magnetic properties of C1 indicated the presence of dominant antiferromagnetic interactions and an S = 0 ground state.

Rational Design of Transition-Metal-Based Catalysts for the Electrochemical 5-Hydroxymethylfurfural Reduction Reaction.

The electrochemical reduction reaction (HMFRR) of 5-hydroxymethylfurfural (HMF) has emerged as a promising avenue for the utilization and refinement of the biomass-derived platform molecule HMF into high-value chemicals, addressing energy sustainability challenges. Transition metal electrocatalysts (TMCs) have recently garnered attention as promising candidates for catalyzing HMFRR, capitalizing on the presence of vacant d orbitals and unpaired d electrons. TMCs play a pivotal role in facilitating the generation of intermediates through interactions with HMF, thereby lowering the activation energy of intricate reactions and significantly augmenting the catalytic reaction rate. In the absence of comprehensive and guiding reviews in this domain, this paper aims to comprehensively summarize the key advancements in the design of transition metal catalysts for HMFRR. It elucidates the mechanisms and pH dependency of various products generated during the electrochemical reduction of HMF, with a specific emphasis on the bond-cleavage angle. Additionally, it offers a detailed introduction to typical in-situ characterization techniques. Finally, the review explores engineering strategies and principles to enhance HMFRR activity using TMCs, particularly focusing on multiphase interface control, crystal face control, and defect engineering control. This review introduces novel concepts to guide the design of HMFRR electrocatalysts, especially TMCs, thus promoting advancements in biomass conversion.

Strategies for the Development of Asymmetric and Non-Directed Petasis Reactions.

 The Petasis reaction is a multicomponent reaction of aldehydes, amines and organoboron reagents and is a useful method for the construction of substituted amines. Despite the significant advancement of the Petasis reaction since its invention in 1993, strategies for asymmetric and non-directed Petasis reactions remain limited. To date, there are very few catalytic asymmetric Petasis reactions and almost all asymmetric reports employ a chiral auxiliary. Likewise, the aldehyde component often requires a directing group, ultimately limiting the reaction's scope. In this concept, key methods for asymmetric and non-directed Petasis reactions are discussed, focusing on how these conceptual advances can be applied to solve long-standing gaps in the Petasis literature.

Compositionally Tunable Mn-V-Fe Phosphoselenide Nanorods with Minimal Ion-Diffusion Barrier as High Energy Density Battery Electrode Materials.

The design and synthesis of novel heterostructured electrode materials are crucial to enable the fabrication of efficient supercapacitor devices. In this regard, transition metal phosphochalcogenides (S, Se) are promising candidates owing to their exotic electronic properties. Herein, a facile two-step hydrothermal protocol was used to synthesize binary and ternary metal phospho-selenide electrodes (Mn-Fe-P-Se, V-Fe-P-Se, Mn-V-P-Se, and Mn-Fe-V-P-Se). The chemical composition, morphology, and structure of the as-fabricated materials were fully investigated. The three-electrode electrochemical evaluation at 1.0 A g-1 demonstrated that the ternary metal electrode (MFVP-Se) exhibits a high capacity of 1968.63 C g-1. To assess the practical value of the rationally designed Mn-Fe-V-P-Se electrode material, Mn-Fe-V-P-Se was used as a positive electrode coupled with activated carbon (AC) as a negative electrode to assemble a hybrid supercapacitor device. This Mn-Fe-V-P-Se//AC device delivers a power density of 1999.96 W kg-1 with a high energy density of 149.88 Wh kg-1 coupled with no capacity loss after 5000 charging/discharging cycles. Additionally, density functional theory calculations revealed that our electrode exhibits suitable adsorption energy for OH- ions with a minimal diffusion barrier for ions.

Multi-Stimuli-Responsive Network of Multicatalytic Reactions using a Single Palladium/Platinum Catalyst.

Given her unrivalled proficiency in the synthesis of all molecules of life, nature has been an endless source of inspiration for developing new strategies in organic chemistry and catalysis. However, one feature that remains thus far beyond chemists' grasp is her unique ability to adapt the productivity of metabolic processes in response to triggers that indicate the temporary need for specific metabolites. To demonstrate the remarkable potential of such stimuli-responsive systems, we present a metabolism-inspired network of multicatalytic processes capable of selectively synthesising a range of products from simple starting materials. Specifically, the network is built of four classes of distinct catalytic reactions-cross-couplings, substitutions, additions, and reductions, involving three organic starting materials-terminal alkyne, aryl iodide, and hydrosilane. All starting materials are either introduced sequentially or added to the system at the same time, with no continuous influx of reagents or efflux of products. All processes in the system are catalysed by a multifunctional heteronuclear PdII/PtII complex, whose performance can be controlled by specific additives and external stimuli. The reaction network exhibits a substantial degree of orthogonality between different pathways, enabling the controllable synthesis of ten distinct products with high efficiency and selectivity through simultaneous triggering and suppression mechanisms.

Trends in hot carrier distribution for disordered noble-transition metal alloys.

We developed and tested an approach for predicting trends for efficient hot carrier generation among disordered metal alloys. We provide a simple argument for the importance of indirect transitions in the presence of disorder, thus justifying the use of joint density of states (JDOS)-like quantities for exploring these trends. We introduce a newJDOS-like quantity,JDOSK, which heuristically accounts for longer lifetimes of quasiparticles close to the Fermi energy. To demonstrate the efficacy of this new quantity, we apply it to the study of Cu50X50where X = Ag, Au, Pd and Y50Pd50where Y = Au, Ni. We predict that Ni50Pd50produces the most hot carriers among the alloys considered. The improvement in the density of excited photocarriers over the base alloy used, Cu50Ag50, is 3.4 times for 800 nm and 19 times for 1550 nm light. This boost in hot-carrier generation is consequence of the ferromagnetic nature of the Ni alloy. We argue that our method allows efficient material-specific predictions for low bias photoconductivity of alloys.

Maxillofacial Reconstruction With Three Dimensional Resin Bone Substitutes as an Alternative to Transition Group of Metals: A Structured Review.

In recent years, novel technologies and techniques have allowed today the production of controlled architecture materials. Although autogenous bone graft substitutes remain the gold standard, enormous defects require supplementary alloplastic substitutes for reconstruction. Polymers have lately been explored for the same purpose and their biological performance has been under research since the last decade. The aim of this review is to analyse maxillofacial reconstruction with three-dimensional resin bone substitutes. A Problem Intervention Comparison Outcomes (PICO) analysis was done and a search was carried out in the Cochrane Database, PubMed, Google Scholar etc databases and a hand search was done to collect the related literature. All articles for maxillofacial reconstruction with three-dimensional resin bone substitutes were scrutinised. The manuscripts published from 1990 till May 2021, were included in this review. A total of 106 articles were obtained from a PICO-based keyword search, and 91 manuscripts were retrieved after excluding the duplicates. Out of these 57 manuscripts were excluded on the basis of title and abstract. From the remaining 34 studies, 17 were excluded after reading the full text based on the inclusion and exclusion criteria. During data extraction, four studies were removed and finally, 13 studies were included in this research. From this scoping review, we could conclude that polymethylmethacrylate and polylactic acid formulations are very promising resin bone substitutes for 3-dimensional reconstruction of maxillofacial defects. However, rigorous long-term clinical trials are needed to validate this conclusion.

Enhanced Heterogeneous Fenton Degradation of Organic Dyes by Bimetallic Zirconia-Based Catalysts.

The qualitative impact of pollutants on water quality is mainly related to their nature and their concentration, but in any case, they determine a strong impact on the involved ecosystems. In particular, refractory organic compounds represent a critical challenge, and several degradation processes have been studied and developed for their removal. Among them, heterogeneous Fenton treatment is a promising technology for wastewater and liquid waste remediation. Here, we have developed mono- and bimetallic formulations based on Co, Cu, Fe, and Mn, which were investigated for the degradation of three model organic dyes (methylene blue, rhodamine B, and malachite green). The treated samples were then analyzed by means of UV-vis spectrophotometry techniques. Bimetallic iron-based materials achieved almost complete degradation of all three model molecules in very short time. The Mn-Fe catalyst resulted in the best formulation with an almost complete degradation of methylene blue and malachite green at pH 5 in 5 min and of rhodamine B at pH 3 in 30 min. The results suggest that these formulations can be applied for the treatment of a broad range of liquid wastes comprising complex and variable organic pollutants. The investigated catalysts are extremely promising when compared to other systems reported in the literature.