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The quest for lowering energy consumption during thin film growth by magnetron sputtering techniques becomes of particular importance in view of sustainable development goals. As large fraction of the process energy is consumed in substrate heating for the purpose of providing high adatom mobility necessary to grow dense films, the most straightforward strategy toward more environment-friendly processing is to find alternatives to thermally activated surface diffusion. One possibility is offered by high mass metal ion irradiation of the growing film surface, which has been recently shown to be very effective in densification of transition metal nitride layers grown with no external heating, such that Zone 2 microstructures of the structure-zone model are obtained in the substrate temperature Ts range otherwise typical for Zone 1 growth. The large mass difference between the incident ion and the atoms constituting the film results in effective creation of low energy recoils, which leads to film densification at low Ts. Due to their high mass, metal ions become incorporated at lattice sites beyond the near-surface region of intense recoil generation leading to further densification, while preventing the buildup of residual stress. The practical implementation of this technique discussed in this Perspective employs heavy metal targets operating in the high-power impulse magnetron sputtering (HiPIMS) mode to provide periodic metal-ion fluxes that are accelerated in the electric field of the substrate to irradiate layers deposited from direct current magnetron sputtering (DCMS) sources. A key feature of this hybrid HiPIMS/DCMS configuration is the substrate bias that is synchronized with heavy metal ion fluxes for selective control of their energy and momentum. As a consequence, the major fraction of process energy is used at sputtering sources and for film densification, rather than for heating of the entire vacuum vessel. Model material systems include TiN and metastable NaCl-structure Ti1−yAlyN films, which are well-known for challenges in stoichiometry and phase stability control, respectively, and are of high relevance for industrial applications. This Perspective provides a comprehensive overview of the novel film growth method. After presenting basic concepts, time-resolved measurements of ion fluxes at the substrate plane, essential for selective control of metal ion energy and momentum, are discussed. The role of metal ion mass, energy, momentum, and concentration is described in more detail. As some applications require substrate rotation for conformal coating, a section is devoted to the related complexity in the implementation of metal-ion-synchronized growth under industrial conditions. [ABSTRACT FROM AUTHOR]

Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence's ionization potential (IP) exceeds the system's double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)n and Mg2+-(H2O)n (n = 1–5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules. The first and second solvation shells are the names for the former and the latter water-binding positions, respectively. For a given n, the lifetime of decaying states is longer when water molecules are in the second solvation shell. We found that the Mg-2p state can decay for all n values in Mg2+-(H2O)n clusters, whereas the Na-2p state's decay is possible for n ≥ 2 in Na+-(H2O)n clusters. Our findings highlight the influence of metal ions' charge, different solvation shell structures, and the number of water molecules on the decay rate. These systems are relevant to the human body, which makes this study significant. [ABSTRACT FROM AUTHOR]

Free iron in human serum or non-transferrin-bound iron (NTBI) can generate free radicals and lead to oxidative damage. Moreover, it is highly toxic to various tissues and a vital biomarker related to the iron-loading status of thalassemia and Alzheimer's patients. In NTBI in healthy individuals, NTBI levels are typically less than 1 µM; current NTBI analysis usually requires advanced instrumentation and many-step sample pretreatment. To address this issue, we employed our invented BODIPY derivative, BODIPY-PH, as a fluorescence probe and trapped it onto the microcentrifuge tube lid using tapioca starch. The fluorescence intensity of BODIPY-PH increased with increasing NTBI concentration (turn-on). The developed portable reaction chamber facilitates rapid analysis (∼5 min) using small sample volumes (10 μL sample in a total volume of 600 μL). Under optimum conditions, using the sample-developed portable fluorescence device and fluorescence spectrometer, we achieved impressive limits of detection (LOD) of 0.003 and 0.0015 μM, respectively. Furthermore, the developed sensors show relatively high selectivity toward Fe3+ over other metal ions and biomolecules (i.e., Fe2+, Cr3+, Cu2+, and glucose). The sensor performance in serum samples of thalassemia patients exhibited no significant difference compared to the labeled value (obtained from standard methods). Overall, the developed fluorescence sensor is suitable for determining NTBI and offers high sensitivity, high selectivity, and a short incubation time (5 min). Moreover, the method requires a limited number of reagents, is simple to use, and uses low-cost equipment to determine NTBI in human serum samples. [ABSTRACT FROM AUTHOR]

Metallosupramolecular architectures formed from metal ions and bridging ligands are increasing in popularity due to their range of applications and ease of self-assembly. Many are able to readily change their shape and/or function in response to an external stimulus and have the ability to encapsulate guest molecules within their internal cavities. Ferrocenyl groups (Fc) have been incorporated previously within the bridging ligands of metallosupramolecular structures due to their ideal attributes brought about by the structural and rotational flexiblity of the two cyclopentadienyl (Cp) rings coordinated to the Fe(II) centre. However, the majority of these Fc-based structures contain symmetrically substituted Cp rings. We report the synthesis and characterisation of non-symmetrically functionalised Fc-based ligands incorporating both N,N' and NHC-donor groups chosen for their differing coordination properties. Both substituents were designed to coordinate to a single metal centre with the dissimilar coordination properties of each donor group facilitating stimulus-induced dissociation/association of one of the substituents as an opening/closing mechanism. Preliminary investigations into the coordination of these Fc-based ligands to a [Ru(6-p-cymene)]2+ moiety indicated complexation through a mixture of either a bi- or tridentate fashion, as alluded by 1H NMR spectroscopy and mass spectrometry. Density functional theory (DFT) calculations revealed the Fc-based ligands adopt a syn conformation driven by H-bonding and p-interactions between the two Cp substituents, which facilitate coordination of both donor groups towards the metal centre. [ABSTRACT FROM AUTHOR]

Due to their unique physical and chemical properties, metal-organic cage structures have great potential for applications in various fields. However, current studies have mainly focused on highly symmetric structures assembled from single metal ions and organic ligands, limiting their diversity and complexity, and there are still relatively few studies on the dynamic formation process of metal-organic cages. Herein, we constructed a series of metal-organic cages with different sizes assembled from the highly-stable coordination of 2,2':6',2"-terpyridine-based tetratopic ligands and various metals ions such as Zn, Cu, Co and Fe. Furthermore, the intermolecular exchange process between the metal-organic cages was explored through the dynamic exchange of ligands, and the formation of a series of hybrid supramolecular nanocages together with their final tendency to form a predominant structure of M24L14L28 was observed. In addition, the binding of metal-organic cages with 5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl) porphyrin-Zn was also investigated. This study not only expands the complexity and diversity of metal-organic cages, but also provides a new perspective for studying the dynamic behaviour of metal-organic cages. [ABSTRACT FROM AUTHOR]

Neurobiological research relies heavily on imaging techniques, such as fluorescence microscopy, to understand neurological function and disease processes. However, the number and variety of fluorescent probes available for ex vivo tissue section imaging limits the advance of research in the field. In this review, we outline the current range of fluorescent probes that are available to researchers for ex vivo brain section imaging, including their physical and chemical characteristics, staining targets, and examples of discoveries for which they have been used. This review is organised into sections based on the biological target of the probe, including subcellular organelles, chemical species (e.g., labile metal ions), and pathological phenomenon (e.g., degenerating cells, aggregated proteins). We hope to inspire further development in this field, given the considerable benefits to be gained by the greater availability of suitably sensitive probes that have specificity for important brain tissue targets. [ABSTRACT FROM AUTHOR]

The use of lignocellulosic biomass to create natural flavor has drawn attention from researchers. A key flavoring ingredient that is frequently utilized in the food industry is vanillin. In this present study, Pediococcus acidilactici PA VIT effectively involved in the production of bio-vanillin by using Ferulic acid as an intermediate with a yield of 11.43 µg/mL. The bio-vanillin produced by Pediococcus acidilactici PA VIT was examined using FTIR, XRD, HPLC, and SEM techniques. These characterizations exhibited a unique fingerprinting signature like that of standard vanillin. Additionally, the one variable at a time method, placket Burmann method, and response surface approach, were employed to optimize bio-vanillin. Based on the central composite rotary design, the most important process factors were determined such as agitation speed, substrate concentration, and inoculum size. After optimization, bio-vanillin was found to have tenfold increase, with a maximum yield of 376.4 µg/mL obtained using the response surface approach. The kinetic study was performed to analyze rate of reaction and effect of metal ions in the production of bio-vanillin showing Km of 10.25, and Vmax of 1250 were required for the reaction. The metal ions that enhance the yield of bio-vanillin are Ca2+, k+, and Mg2+ and the metal ions that affects the yield of bio-vanillin are Pb+ and Cr+ were identified from the effect of metal ions in the bio-vanillin production. • Identification and characterization of Pediococcus Acidilactici capable of catalyzing the production of bio vanillin. • Optimization of fermentation conditions to enhance the biotransformation efficiency and yield of vanillin. • Evaluating bio-vanillin produced through biotransformation, demonstrating its suitability for various applications. • A detailed kinetic study, shedding light on the reaction rates involved in the process of bio vanillin production. [ABSTRACT FROM AUTHOR]

In this work, a horseradish peroxidase (HRP)‐encapsulated metal organic framework (MOF)@MOF nanocomposite is developed for detecting H2O2 converted by dismutation of superoxide anions released from live HeLa mitochondria. Initially, an HRP‐polyacrylic acid cluster is incorporated on a mesoporous, peroxidase‐like Cu/Co‐1,4‐benzenedicarboxylate (BDC) MOF platform to avoid structural change and deactivation of HRP through its interactions with MOF metal ions. Additionally, a Cu/Co‐BDC(HRP)@1,3,5‐benzenetricarboxyate (BTC) core‐shell MOF/MOF structure, also with peroxide‐like properties, serves as a protective matrix for HRP. Then, ultrathin porous carbon shells (UPCS) are adopted to improve the electrical conductivity of the MOF@MOF. The Cu/Co‐BDC(HRP)@BTC|UPCS sensing platform exhibits two linear ranges of 0.05–1 µM and 1–1000 µM with a sensitivity of 172 mA mM−1 cm−2 and 1.63 mA mM−1 cm−2, respectively. A limit of detection of 0.057 µM, good selectivity and stability over 35 days for H2O2 detection are also achieved. After treating the mitochondrial complex with specific inhibitors, amperometric results at the sensing platform confirmed complex I and III within mitochondria as the main electron leakage sites in the electron transfer chains. Therefore, this sensing platform provides a tool that may aid in predicting and even developing treatments for some oxidative stress diseases caused by mitochondrial abnormalities. [ABSTRACT FROM AUTHOR]

The cost‐effectiveness and environmental benefits of aqueous zinc‐ion batteries (ZIBs) have attracted considerable attention. However, practical applications are hindered by side processes including dendritic growth and hydrogen evolution corrosion. Herein, gallium ions (Ga3+) have been chosen as a multifunctional electrolyte additive to improve the reversibility of zinc‐ion batteries (ZIBs). Remarkably, Ga3+ ions adhere to the anode surface, establishing a dynamic electrostatic shielding layer that modulates Zn2+ deposition and prevents side reactions. Typically, Ga3+ ions preferentially adsorb onto the (002) and (110) planes of Zn, facilitating preferential deposition on the (100) plane, resulting in a dendrites‐free zinc anode. Consequently, the Zn||Zn symmetrical cell with Ga3+‐modified electrolyte demonstrates a prolonged lifespan of 4000 h, while the Zn||Ti asymmetric cell exhibits an impressive coulombic efficiency of 99.12% for zinc stripping and plating at 2 mA cm−2. Additionally, the Zn||VO2 cell maintains high capacity retention after 1500 cycles at 5 A g−1. This work presents Ga3+ ions as an electrolyte additive, facilitating the development of a durable dynamic electrostatic shielding effect and preferential (100) plane electroplating, ensuring zinc deposition free from dendrite formation. Such discoveries form a basis for future investigations into novel materials to propel advancements in metal battery technology. [ABSTRACT FROM AUTHOR]

Mercury and lead toxicity in water has serious repercussions on human health. There is an urgent need to develop effective and efficient small moieties for their removal. The convenient one-pot synthesis of a few N3Se3 type small sized moieties is reported herein. The highest metal ion uptake capacity of Hg(II) and Pb(II) ions was found to be 314.3 mg g−1 and 93.5 mg g−1, respectively, by ICP-MS analysis. These ion uptake values are the highest for small sized moieties known in the literature to date. [ABSTRACT FROM AUTHOR]

Despite the excellent thermometric performance of many developed luminescent nanomaterials, their use has not gone beyond proof‐of‐concept in vivo experiments to date. An important issue that needs to be resolved before moving toward true biomedical applications of engineered nanothermometers is their potential toxicity and bioaccumulation in the human body considering the ultimate objective of clinical applications. Since most reported nanothermometers currently are not degradable materials and are mainly based on the incorporation of heavy metal ions, these aspects remain of genuine concern in the fields of nanomedicine, nanobiotechnology, nanotoxicology, and nanopharmacology. This work explores the possibility of designing visible, as well as near‐infrared, emitting luminescent ratiometric nanothermometers based on appropriate organic dye mixtures embedded in hollow disulfide‐bridged periodic mesoporous organosilica (PMO) particles. Such hybrid particles show excellent thermometric performance in the physiological temperature range (20–50 °C), favorable degradability in simulated physiological conditions, as well as no toxicity to healthy normal human dermal fibroblast (NHDF) cells in a wide concentration range. Considering the simplicity of the approach from the synthetic point of view, and the large available library of known fluorescent dyes emitting in various regions of the electromagnetic range, this motif renders a very promising approach to designing novel non‐toxic, decomposable, luminescent ratiometric thermometers. [ABSTRACT FROM AUTHOR]

The utilization of advanced photothermal materials for personal thermal management to improve thermal comfort and regulate heat exchange between the human body and the environment is a focal point of research. Herein, this study presents the design of in situ metal-ion-incorporated photothermal GO films with high light capture efficiency (98.51% of GO--Fe-0.3 film) and exceptional photothermal conversion capability (~61.3 °C under 1 solar illumination), offering temperature adjustability within the range of 39.1--61.3 °C. This temperature adjustability is facilitated by the straightforward control of the metal ion content, which enables versatile applications in daily human thermal regulation and high-temperature medical contexts. Furthermore, this strategy demonstrates scalability and flexibility through the variation of metal ion types. Practical simulations using a tailored flexible and wearable device reveal a rapid temperature increase of ~61.5 °C within 600 s. Therefore, the in situ metal-ion-incorporated photothermal GO films exhibit significant potential in advancing photothermal conversion for adaptable personal thermal management. [ABSTRACT FROM AUTHOR]

Based on the strong binding properties of hydroxylamino-1,3,5-triazine (BHT) for hard metal ions, a novel spectroscopically labelled triazine-hydroxylaminato ligand, N,N′-(6-(9H-carbazol-9-yl)-1,3,5-triazine-2,4-diyl)bis(N-methylhydroxylamine) (H2cbht), was synthesized. Reaction of H2cbht with FeIII, VV and UVI resulted in the synthesis of [UVIO2(cbht)(DMF)(MeOH)], 1, (PPh4)2([UVIO2(Hcbht)2]·2[UVIO2(Hcbht)(cbht)]), 2, (PPh4)2[(UVIO2)3(μ-cbht)2(cbht)2], 3, Na[VVO2(cbht)], 4, and (PPh4)[FeIII(cbht)2], 5. The complexes were characterized by X-ray crystallography showing strong chelation of the metal ions with the BHT chelating moiety H2cbht. The DMSO/DMF solutions of the complexes were characterized by NMR, UV-vis and electrochemistry, confirming the high affinity of H2cbht for FeIII, VV or UVI. The luminescence properties of the carbazole group were retained in the BHT adduct of the H2cbht ligand. Interaction of the metal ions with H2cbht resulted in quenching of the luminescence of H2cbht. Stern–Volmer plots of luminescence vs. concentration of the metal ions are linear and suitable for the determination of the concentration of metal ions in nM range concentrations. Benesi–Hildebrand plots show that the metal-to-ligand ratio is 1 : 1 while the formation of the metal complexes exhibits high association constants. [ABSTRACT FROM AUTHOR]

Herein, a disubstitution strategy of metal ions and organic ligands is employed to synthesize metal–organic framework (MOF) nanosheets with a three-dimensional (3D) porous structure and a highly active metal–sulfur (M–S, M = Co and Ni) region. The obtained MOFs//Zn batteries exhibit excellent electrochemical properties and the electrochemical reaction mechanism was elucidated through a series of ex situ characterizations. [ABSTRACT FROM AUTHOR]

A new palladium(II) complex containing the previously synthesized 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane ligand maltonis was prepared and characterized both in solution and in the solid state. Hirshfeld surface and energy framework analyses were also performed. Because maltonis already showed antineoplastic activity, the complexation of Pd(II), chosen as an alternative to Pt(II), was investigated to study its possible biological activity. UV-vis and NMR studies confirmed the formation and stability of the complex in aqueous solution at physiological pH. X-ray diffraction data revealed a structure where the Pd(II) ion is lodged in the dimethyl-cyclen cavity, with maltol rings facing each other (closed shape) even if they are not involved in the coordination. DFT analysis was performed in order to understand the most stable shape of the complex. In view of evaluating its possible bioactive conformation, the DFT study suggested a slight energetic preference for the closed one. The resulting closed complex was stabilized in the X-ray structure by intermolecular interactions that replace the intramolecular interactions present in the optimized complex. According to the DFT calculated formation energies, notwithstanding its rarity, the Pd(II) complex of maltonis is the thermodynamically preferred one among analogous complexes containing different metal ions (Pt(II), Co(II), and Cu(II)). Finally, to study its possible biological activity, the interaction between the Pd(II) complex of maltonis and nucleosides was evaluated through NMR and DFT calculations, revealing a possible interaction with purines via the maltol moieties. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries (ZIBs) have attracted enormous attention for future energy-storage devices owing to their high theoretical capacity and environmental friendliness. However, obtaining cathodes with a high specific capacity and fast reaction kinetics remains a huge challenge. Herein, Cu-VOx material with a thin sheet microsphere structure composed of nanoparticles was prepared by a simple hydrothermal reaction, which improved reaction kinetics and specific capacity. Pre-embedding Cu2+ into V2O5 to introduce abundant oxygen vacancies extended the interlayer distance to 1.16 nm, weakened the effect of the V-O bonds, and improved the electrical conductivity and structural stability. At the same time, the influence of different valence metal ions (M = K+, Cu2+, Fe3+, Sn4+, Nb5+, and W6+) pre-embedded in V2O5 was studied. Benefiting from a large interlayer spacing, high electrical conductivity, and excellent structural stability, the Cu-VOx electrode demonstrated a high specific capacity of 455.9 mAhg-1 at 0.1 A g-1. Importantly, when the current density was increased to 6 A g-1,the Cu-VOx electrode still achieved a high specific capacity of 178.8 mA h g-1 and maintained a high capacity retention of 76.5% over 2000 cycles. [ABSTRACT FROM AUTHOR]

AbstractThe emergence of calixarenes as versatile compounds in recent years marks a significant advancement in scientific research. In the area of analytical chemistry, calixarenes have garnered attention for their utility as selective chemosensors, enabling the sensitive and specific detection of metal ions through colorimetric and fluorimetric methods. Moreover, calixarenes have found applications in bioimaging, where they serve as effective probes for visualizing biological structures and processes with high resolution and sensitivity. Additionally, recent studies have explored the anticancer properties of calixarenes, unveiling their potential as therapeutic agents for cancer treatment. This comprehensive review explores recent advancements in calixarenes chemistry, emphasizing their significance in the colorimetric and fluorimetric detection of metal ions. Additionally, it highlights the mechanisms involved in chemosensor design, providing insights into the underlying principles driving their efficacy. Furthermore, the application of calixarenes in bioimaging, particularly for visualizing cellular structures and processes, is discussed, showing their potential in biomedical research and diagnostics. The anticancer activity of calixarenes and their derivatives is also explored, shedding light on their promising role as therapeutic agents. Through an extensive examination of recent literature, this review provides valuable insights into the multifaceted applications of calixarenes and offers perspectives for future research directions. [ABSTRACT FROM AUTHOR]

This study explores the complexation behavior of previously unexplored N7-alkylated 6-chloropurine derivatives with group 12 metal cations (Zn2+, Cd2+, and Hg2+), where N9 is free to coordinate. Notably, with high basicity, the N9 nitrogen atoms serve as the primary coordination sites for all investigated metal ions. The N1 position does not coordinate with any metal ions under this study. Interestingly, N3 participates in binding with Cd2+ and Hg2+ ions, resulting in the formation of a 1D linear coordination polymer bridged by chloride anions. The observed polymeric structure exhibits further extension through intermolecular non-classical hydrogen bonding and π–π stacking interactions. In contrast, Zn2+ forms discrete coordination complexes that extend in the lattice due to hydrogen bonding interactions. The observed consistency in coordination preferences of metal–purine complexes translates to predictable motifs, and this reliable binding can serve as a synthon for the targeted construction of MOFs. [ABSTRACT FROM AUTHOR]

Paper-based microfluidics combined with potentiometric measurement has emerged as an attractive approach for detecting various chemical ionic moieties. Detection of heavy metal ions, using paper substrates as solution sampling and delivery systems remains challenging despite efforts to introduce several physico-chemical paper substrate modifications to stop adsorption of ions onto the paper substrates. This study quantitatively investigates the adsorption of heavy metal ions on the paper substrates during paper-based potentiometric measurements and explains the super-Nernstian response of potentiometric sensors through local depletion of heavy metal ions from the solution. Consequently, based on the investigated ion adsorption, a corrective potential protocol was established for the electrodes coupled with paper-based solution sampling by predicting interference free sensor response from paper-based measurement. Furthermore, the ion adsorption was also recorded for mixed metal ion solutions to understand competitive primary/interfering ions adsorption onto the paper substrates and establish corrective measures to predict interference free sensor response. In this method, no modifications of the paper substrates are necessary before actual potentiometric measurements. The proposed corrective protocol allows prediction of sensor response based on the paper-based solution sampling potentiometric measurement, providing a simple methodological approach based on correction of potential readout of the potentiometric sensor, thus completely resigning from the need of modifying paper substrate for measurements of heavy metal ions. [ABSTRACT FROM AUTHOR]

The influence of dopant molecules on the structure and functionality of spin-crossover (SCO) materials is surveyed. Two aspects of the topic are well established. Firstly, isomorphous inert metal ion dopants in SCO lattices are a useful probe of the energetics of SCO processes. Secondly, molecular alloys of iron(II)/triazole coordination polymers containing mixtures of ligands were used to tune their spin-transitions towards room temperature. More recent examples of these and related materials are discussed that reveal new insights into these questions. Complexes which are not isomorphous can also be co-crystallised, either as solid solutions of the precursor molecules or as a random distribution of homo- and hetero-leptic centres in a molecular alloy. This could be a powerful method to manipulate SCO functionality. Published molecular alloys show different SCO behaviours, which may or may not include allosteric switching of their chemically distinct metal sites. [ABSTRACT FROM AUTHOR]

Understanding the functions of metal ions in biological systems is crucial for many aspects of research, including deciphering their roles in diseases and potential therapeutic use. Structural information about the molecular or atomic details of these interactions, generated by methods like X-ray crystallography, cryo-electron microscopy, or nucleic magnetic resonance, frequently provides details that no other method can. As with any experimental method, they have inherent limitations that sometimes lead to an erroneous interpretation. This manuscript highlights different aspects of structural data available for metal-protein complexes. We examine the quality of modeling metal ion binding sites across different structure determination methods, where different kinds of errors stem from, and how they can impact correct interpretations and conclusions. [ABSTRACT FROM AUTHOR]

Heavy metal ions can be introduced into the water through several point and non-point sources including leather industry, coal mining, agriculture activity and domestic waste. Regrettably, these toxic heavy metals may pose a threat to both humans and animals, particularly when they infiltrate water and soil. Heavy metal poisoning can lead to many health complications, such as liver and renal dysfunction, dermatological difficulties, and potentially even malignancies. To mitigate the risk of heavy metal ion exposure to humans and animals, it is imperative to extract them from places that have been polluted. Several conventional methods such as ion exchange, reverse osmosis, ultrafiltration, membrane filtration and chemical precipitation have been used for the removal of heavy metal ions. However, these methods have high operation costs and generate secondary pollutants during water treatment. Biosorption is an alternative approach to eliminating heavy metals from water that involves employing eco-friendly and cost-effective biomass. This review is focused on the heavy metal ions contamination in the water, biosorption methods for heavy metal removal and mathematical modeling to explain the behaviour of heavy metal adsorption. This review can be helpful to the researchers to design wastewater treatment plants for sustainable wastewater treatment. [ABSTRACT FROM AUTHOR]

Two‐dimensional Ti3C2Tx MXene materials, with metal‐like conductivities and versatile terminals, have been considered to be promising surface modification materials for Zn‐metal‐based aqueous batteries (ZABs). However, the oxygen‐rich and hybridized terminations caused by conventional methods limit their advantages in inhibiting zinc dendrite growth and reducing corrosion‐related side reactions. Herein, −O‐depleted, −Cl‐terminated Ti3C2Tx was precisely fabricated by the molten salt electrochemical etching of Ti3AlC2, and controlled in situ terminal replacement from −Cl to unitary −S or −Se was achieved. The as‐prepared −O‐depleted and unitary‐terminal Ti3C2Tx as Zn anode coatings provided excellent hydrophobicity and enriched zinc‐ionophilic sites, facilitating Zn2+ horizontal transport for homogeneous deposition and effectively suppressing water‐induced side reactions. The as‐assembled Ti3C2Sx@Zn symmetric cell achieved a cycle life of up to 4200 h at a current density and areal capacity of 2 mA cm−2 and 1 mAh cm−2, respectively, with an impressive cumulative capacity of up to 7.25 Ah cm−2 at 5 mA cm−2//2 mAh cm−2. These findings provide an effective electrochemical strategy for tailoring −O‐depleted and unitary Ti3C2Tx surface terminals and advancing the understanding of the role of specific Ti3C2Tx surface chemistry in regulating the plating/stripping behaviors of metal ions. [ABSTRACT FROM AUTHOR]

Acid-leached gangue residue is produced after the gangue extraction of metal ions; the main component is silicon, which can be used to extract silica. To ascertain the kinetics and mechanism of silica extraction from acid-leached coal gangue residue, this study explored the effects of the NaOH concentration, solid-to-liquid ratio, reaction temperature, and reaction time on the extraction process. The optimized conditions, determined through this investigation, involved a NaOH concentration of 4 mol/L, a reaction time of 4 h, a solid-to-liquid ratio of 1:4, and a reaction temperature of 180 °C, yielding a SiO2 extraction ratio of 90.16%. Additionally, the leaching kinetics of silica in a NaOH solution were examined using three kinetic equations from the "unreacted shrinking core model". The results revealed that the control type of the leaching process was the "mixing control", and the apparent activation energy was determined to be 52.36 kJ/mol. [ABSTRACT FROM AUTHOR]

The aim of this study was to develop new materials with adsorbent properties that can be used for the adsorption recovery of Au(III) from aqueous solutions. To achieve this result, it is necessary to obtain inexpensive adsorbent materials in a granular form. Concomitantly, these materials must have a high adsorption capacity and selectivity. Other desired properties of these materials include a higher physical resistance, insolubility in water, and materials that can be regenerated or reused. Among the methods applied for the separation, purification, and preconcentration of platinum-group metal ions, adsorption is recognised as one of the most promising methods because of its simplicity, high efficiency, and wide availability. The studies were carried out using three supports: cellulose (CE), chitosan (Chi), and diatomea earth (Diat). These supports were functionalised by impregnation with extractants, using the ultrasound method. The extractants are environmentally friendly and relatively cheap amino acids, which contain in their structure pendant groups with nitrogen and sulphur heteroatoms (aspartic acid—Asp, l-glutamic acid—Glu, valine—Val, DL-cysteine—Cys, or serine—Ser). After preliminary testing from 75 synthesised materials, CE-Cys was chosen for the further recovery of Au(III) ions from aqueous solutions. To highlight the morphology and the functionalisation of the material, we physicochemically characterised the obtained material. Therefore, the analysis of the specific surface and porosity showed that the CE-Cys material has a specific surface of 4.6 m2/g, with a porosity of about 3 nm. The FT-IR analysis showed the presence, at a wavelength of 3340 cm−1, of the specific NH bond vibration for cysteine. At the same time, pHpZc was determined to be 2.8. The kinetic, thermodynamic, and equilibrium studies showed that the pseudo-second-order kinetic model best describes the adsorption process of Au(III) ions on the CE-Cys material. A maximum adsorption capacity of 12.18 mg per gram of the adsorbent material was achieved. It was established that the CE-Cys material can be reused five times with a good recovery degree. [ABSTRACT FROM AUTHOR]

Sample preparation is one of the viable procedures to be used before analysis to enhance sensitivity and reduce the matrix effect. The current review is mainly emphasized the latest outcome and applications of microextraction techniques based on the miniaturization of the classical conventional methods based on liquid-phase and solid-phase extraction for the quantitative elemental analysis in different real samples. The limitation of the conventional sample preparation methods (liquid and solid phase extraction) has been overcome by developing a new way of reducing size as compared with the conventional system through the miniaturization approach. Miniaturization of the sample preparation techniques has received extensive attention due to its extraction at microlevels, speedy, economical, eco-friendly, and high extraction capability. The growing demand for speedy, economically feasible, and environmentally sound analytical approaches is the main intention to upgrade the conventional procedures apply for sample preparation in environmental investigation. A growing trend of research has been perceived to quantify the trace for elemental analysis in different natures of real samples. This review also recapitulates the current futuristic scenarios for the green and economically viable procedure with special overemphasis and concentrates on eco-friendly miniaturized sample-preparation techniques such as liquid-phase microextraction (LPME) and solid-phase microextraction (SPME). This review also emphasizes the latest progress and applications of the LPME and SPME approach and their future perspective. [ABSTRACT FROM AUTHOR]

Organic compounds display several electronic and structural features which enable their application in various fields, ranging from biological to non-biological. These compounds contain heteroatoms like sulfur, nitrogen and oxygen, which provide coordination sites to act as ligands in the field of coordination chemistry and are used as chemosensors to detect various metal ions. This review article covers different organic compounds including thiourea, Schiff base, pyridine, thiophene, coumarin, triazolyl pyrenes, imidazole, fluorescein, thiazole, tricarbocyanine, rhodanine, porphyrin, hydrazone, benzidine and other functional groups based chemosensors, that contain heteroatoms like sulfur, nitrogen and, oxygen for fluorimetric and colorimetric detection of Ag+ in different environmental, agricultural, and biological samples. Further, the sensing mechanism and performances of these chemosensors have been discussed, which could help the readers for the future design of highly efficient, selective, and sensitive chemosensors for the detection and determination of Ag+ ions. [ABSTRACT FROM AUTHOR]

Heavy metals ions as metallic pollutants are a growing global issue due to their adverse effects on the aquatic ecosystem, and human health. Unfortunately, conventional detection methods such as atomic absorption spectrometry exhibit a relatively low limit of detection and hold numerous disadvantages, and therefore, the development of an efficient method for in-situ and real-time detection of heavy metal residues is of great importance. The aptamer-based sensors offer distinct advantages over antibodies and emerged as a robust sensing platform against various heavy metals due to their high sensitivity, ease of production, simple operations, excellent specificity, better stability, low immunogenicity, and cost-effectiveness. The nucleic acid aptamers in conjugation with nanomaterials can bind to the metal ions with good specificity/selectivity and can be used for on-site monitoring of metal ion residues. This review aimed to provide background information about nanomaterials-based aptasensor, recent advancements in aptamer conjunction on nanomaterials surface, the role of nanomaterials in improving signal transduction, recent progress of nanomaterials-based aptasening procedures (from 2010 to 2022), and future perspectives toward the practical applications of nanomaterials-based aptasensors against hazardous metal ions for food safety and environmental monitoring. [ABSTRACT FROM AUTHOR]

This study explores the purification and impact of metal ions on Aspergillus niger tannase, a metalloenzyme. Gel permeation chromatography achieved a 22.03-fold purification, yielding a specific activity of 106 U/mg. The enzyme, confirmed as a homodimer (100 kDa native, 50 kDa SDS PAGE), exhibited enhanced activity in the presence of calcium ions, reaching 163.46 U/mg, a 1.42-fold increase. UV absorption with 6 µM Ca ions indicated structural stability. Kinetic studies revealed a sigmoidal Michaelis–Menten graph with calcium ions, suggesting allosteric effects. The Lineweaver–Burk plot showed increased Km (14.04 to 36.39 mM) with mercuric ions, indicating competitive inhibition, while Vmax remained stable. Reactivation studies with DTT and different metal ions showed maximum reactivation with Hg (88.8%) and Ag (81.4%), implicating binding with cysteine residue in inactivation. EDTA-induced reactivation displayed maximum reactivation with Cu ions (67.6%) and minimum with Hg (22.5%), indicating Cu ions form complexes with amino acid groups. In contrast, Hg forms a coordination sphere with the thiol group of a cysteine residue. This comprehensive examination provides insights for optimizing tannase-based processes in various industries and expanding its biotechnological applications. [ABSTRACT FROM AUTHOR]

[Display omitted] Understanding the structure-function relationships encoded on chiral catalysts is important for investigating the fundamental principles of catalytic enantioselectivity. Herein, the synthesis and self-assembly of naphthalene substituted bis - l / d -histidine amphiphiles (bis - l / d - NapHis) in DMF/water solution mixture is reported. The resulting supramolecular assemblies featuring well-defined P/M nanoribbons (NRs). With combination of the (P/M)-NR and metal ion catalytic centers (M n+ = Co2+, Cu2+, Fe3+), the (P)-NR-M n+ as chiral supramolecular catalysts show catalytic preference to 3,4-dihydroxy- S -phenylalanine (S -DOPA) oxidation while the (M)-NR-M n+ show enantioselective bias to R -DOPA oxidation. In contrast, their monomeric counterparts bis - l / d - NapHis-M n+ display an inverse and dramatically lower catalytic selectivity in the R/S -DOPA oxidation. Among them, the Co2+-coordinated supramolecular nanostructures show the highest catalytic efficiency and enantioselectivity (select factor up to 2.70), while the Fe3+-coordinated monomeric ones show nearly racemic products. Analysis of the kinetic results suggests that the synergistic effect between metal ions and the chiral supramolecular NRs can significantly regulate the enantioselective catalytic activity, while the metal ion-mediated monomeric bis - l / d - NapHis were less active. The studies on association constants and activation energies reveal the difference in catalytic efficiency and enantioselectivity resulting from the different energy barriers and binding affinities existed between the chiral molecular/supramolecular structures and R/S -DOPA enantiomers. This work clarifies the correlation between chiral molecular/supramolecular structures and enantioselective catalytic activity, shedding new light on the rational design of chiral catalysts with outstanding enantioselectivity. [ABSTRACT FROM AUTHOR]

Using NaN3 and a chiral N-donor ligand (1R,2R)-1,2-diphenylethylenediamine (L) to react with Co(ClO4)2(H2O)6 and Ni(ClO4)2(H2O)6, respectively, two chiral CoIII and NiII complexes with formulae [Co(L)2(N3)2](ClO4)(0.5H2O) (1) and [Ni(L)2(μ1,3-N3)]n(ClO4)n(0.5H2O)n (2) were isolated and structurally characterized. Although 1 and 2 contain the same L and N3− ligands, they have completely different molecular structures. 1 shows a chiral mononuclear structure with N3− as the terminal ligand, in which the CoII ion has been oxidized to the CoIII ion, while 2 exhibits a chiral one-dimensional (1D) NiII chain structure with N3− as the bridging ligand. Notably, a study of their nonlinear optical (NLO) properties demonstrates that 1 presents a moderate second-harmonic generation (SHG) response (0.15 × KDP), while 2 only displays a strong third-harmonic generation (THG) response (160 × α-SiO2). This interesting finding gives the first example of the complexes with the same ligands but different molecular structures showing completely different NLO responses regulated by metal ions. [ABSTRACT FROM AUTHOR]

Herein, we successfully fabricated ultra-small metal nanoparticles into two stable Zr-based metal–organic frameworks via in situ redox reactions between triphenylamine and the corresponding metal ions to afford Pd NPs@1 and Pd NPs@2, which exhibit excellent activity and reusability for Suzuki coupling reactions as heterogeneous catalysts. [ABSTRACT FROM AUTHOR]

ABSTRACT This study introduces a new electrochemical sensor for bisphenol A (BPA) and metal ions utilizing a microsphere dual‐ligand Ni‐based MOFs modified carbon paste. The MOFs (Ni‐bipy‐btc) synthesized from dual‐ligands were prepared via a hydrothermal method and characterized using X‐ray diffraction (XRD), scanning electron microscope (SEM), FT‐IR spectrometer, X‐ray photoelectron spectrum (XPS), and specific surface area test (BET) analysis. The resulting MOFs exhibited promising performance as electrode materials for electrochemical sensors targeting the detection of BPA and heavy metal ions (Pb2+ and Cu2+). The linear range of the MOFs (Ni‐bipy‐btc)/CPE electrode for BPA detection ranged from 0.2 to 150 μM, with a detection limit of 0.045 μM, demonstrating robust immunity and stability. Additionally, the limit of detection for the MOFs (Ni‐bipy‐btc)/CPE electrode was found to be 4.3 and 9.5 nM for Pb2+ and Cu2+ ions, respectively, showcasing excellent stability and reproducibility. This study presents a straightforward approach for the highly sensitive electrochemical detection of BPA and heavy metal ions using a simple hydrothermal reaction method. [ABSTRACT FROM AUTHOR]

Metal ion (Mn+ ${{{\rm M}}^{{\rm n}+}}$ /oxidant) and UV light catalyzed (UV/oxidant) mineralization and biodetoxification of Ponceau Xylidine (PX) was undertaken in this study. Hydrogen peroxide (HP) and ammonium persulphate (APS) were employed as oxidants and Fe2+ ${{{\rm F}{\rm e}}^{2+}}$ and Ag+ ${{{\rm A}{\rm g}}^{+}}$ as metal ion catalysts. Although highest mineralization in Fe2+ ${{{\rm F}{\rm e}}^{2+}}$ /APS and UV/HP systems was exhibited at pH 1 (63.09 %) and 3 (64.83 %), respectively, lowest was shown by Ag+ ${{{\rm A}{\rm g}}^{+}}$ /oxidant systems at any pH. The Fenton process achieved mineralization of ≈48.50 % within the pH range of 3 to 6.15. The study established Fe2+ ${{{\rm F}{\rm e}}^{2+}}$ as a better catalyst than Ag+ ${{{\rm A}{\rm g}}^{+}}$ , and HP, a better oxidant (2.5 times more effective) than APS. Mineralization with UV/HP at 120 min is highest at pH 3 (92.0 %) and 6.15 (86.17 %). Various inorganic anions were found to inhibit mineralization. The maximum and minimum inhibition was shown by Cl- ${{{\rm \ }{\rm C}{\rm l}}^{-}}$ in UV/HP and UV/APS systems respectively. The inhibition effect of NO3- ${{{\rm N}{\rm O}}_{3}^{-}}$ decreases with concentration till 0.01 mM, beyond which an increasing trend was observed. This study also demonstrates that the biodetoxification efficiency of various systems is in the order: UV/HP>UV/APS>Fe2+ ${{{\rm F}{\rm e}}^{2+}}$ /HP. Thus, UV/HP is the most suitable system for the treatment of PX, displaying a biodetoxification efficiency of 83.0 % and mineralization of 92.0 %. [ABSTRACT FROM AUTHOR]

Copper chaperones of the ATX1 family are found in a wide range of organisms where these essential soluble carriers strictly control the transport of monovalent copper across the cytoplasm to various targets in diverse cellular compartments thereby preventing detrimental radical formation catalyzed by the free metal ion. Notably, the ATX1 family in plants contains two distinct forms of the cellular copper carrier. In addition to ATX1 having orthologs in other species, they also contain the copper chaperone CCH. The latter features an extra C-terminal extension whose function is still unknown. The secondary structure of this extension was predicted to be disordered in previous studies, although this has not been experimentally confirmed. Solution NMR studies on purified CCH presented in this study disclose that this region is intrinsically disordered regardless of the chaperone's copper loading state. Further biophysical analyses of the purified metallochaperone provide evidence that the C-terminal extension stabilizes chaperone dimerization in the copper-free and copper-bound states. A variant of CCH lacking the C-terminal extension, termed CCHΔ, shows weaker dimerization but similar copper binding. Computational studies further corroborate the stabilizing role of the C-terminal extension in chaperone dimerization and identify key residues that are vital to maintaining dimer stability. [ABSTRACT FROM AUTHOR]

Wood‐derived carbons demonstrate great potential as self‐standing electrodes in energy storage/conversion applications, including supercapacitors and water‐splitting devices. However, the key challenge remains the rational customization of surface functionalities for optimized performance. This study introduces an innovative approach to self‐standing wood‐derived carbons with tailored nitrogen and metal functionalities. In contrast to traditional impregnation techniques, which offer limited precision in surface modification, this approach entails the intentional attachment of amidoxime groups to the wood substrates. These groups serve as nitrogen sources, and create abundant surface anchoring sites for metal ions due to the chelation between the amidoxime groups and metals. The resulting carbons feature uniform and high dispersion of nitrogen and metal functionalities, along with a distinctive hierarchical porosity combining interconnected open channels with abundant mesopores. As a proof‐of‐concept, different metals are incorporated (i.e., Mn, Co, Ni) into the amidoximated‐wood precursors, and the resulting self‐standing carbons showcase excellent performance in both supercapacitors and water‐splitting applications. Leveraging the specific chelating ability of amidoxime groups toward metal ions, this strategy holds great potential as a generic approach to systematically tailoring the surface functionalities of carbon‐based materials for various electrochemical energy storage/conversion processes. [ABSTRACT FROM AUTHOR]

ABSTRACT The coordination polymer {[Cu6(CN)6]·HPD}n, CP1; (HPD = heptane‐1,7‐diamine) was prepared and characterized by single‐crystal and powder X‐ray diffraction, UV–Vis spectroscopy, electron microscopy (TEM and SEM), and elemental analyses. The copper atoms are coordinated by C ≡ N ligands, and both exhibit tetrahedral geometry. Cu1 and Cu2 create the pretty unique cluster structure of two quadruple [Cu2(μ3‐CN)2] units exhibiting coprophilic interaction. The building blocks [Cu3(CN)3]2 form fused distorted rectangular rings surrounded with the [Cu2(μ3‐CN)2] motifs exhibiting wide voids to accommodate the guest HPD. The structure of 1 indicates the formation of channels with dimensions 5.121–8.469 Ǻ which extend three‐dimensionally creating fused cavity morphology with different shapes. CP1 was utilized as an efficient sensor for selective quantitative estimation of metal ions (Co2+) and explosives (NB). Advanced oxidation process (AOP) was used as an efficient photocatalyst for the removal of the antibiotic meloxicam (MEL) utilizing AOP in the presence of H2O2 as an oxidant. Scavenge experiments, reusability of catalyst 1, and mechanism of oxidation were also discussed. [ABSTRACT FROM AUTHOR]

Metal-ion-dependent nucleases play crucial roles in cellular defense and biotechnological applications. Time-resolved crystallography has resolved catalytic details of metal-ion-dependent DNA hydrolysis and synthesis, uncovering the essential roles of multiple metal ions during catalysis. The histidine-metal (His-Me) superfamily nucleases are renowned for binding one divalent metal ion and requiring a conserved histidine to promote catalysis. Many His-Me family nucleases, including homing endonucleases and Cas9 nuclease, have been adapted for biotechnological and biomedical applications. However, it remains unclear how the single metal ion in His-Me nucleases, together with the histidine, promotes water deprotonation, nucleophilic attack, and phosphodiester bond breakage. By observing DNA hydrolysis in crystallo with His-Me I-PpoI nuclease as a model system, we proved that only one divalent metal ion is required during its catalysis. Moreover, we uncovered several possible deprotonation pathways for the nucleophilic water. Interestingly, binding of the single metal ion and water deprotonation are concerted during catalysis. Our results reveal catalytic details of His-Me nucleases, which is distinct from multi-metal-ion-dependent DNA polymerases and nucleases. [ABSTRACT FROM AUTHOR]

Aqueous zinc ion batteries (AZIBs) have received a lot of attention in electrochemical energy storage systems for their low cost, environmental compatibility, and good safety. However, cathode materials still face poor material stability and conductivity, which cause poor reversibility and poor rate performance in AZIBs. Herein, a heterogeneous structure combined with cation pre-intercalation strategies was used to prepare a novel CaV6O16·3H2O@Ni0.24V2O5·nH2O material (CaNiVO) for high-performance Zn storage. Excellent energy storage performance was achieved via the wide interlayer conductive network originating from the interlayer-embedded metal ions and heterointerfaces of the two-phase CaNiVO. Furthermore, this unique structure further showed excellent structural stability and led to fast electron/ion transport dynamics. Benefiting from the heterogeneous structure and cation pre-intercalation strategies, the CaNiVO electrodes showed an impressive specific capacity of 334.7 mAh g−1 at 0.1 A g−1 and a rate performance of 110.3 mAh g−1 at 2 A g−1. Therefore, this paper provides a feasible strategy for designing and optimizing cathode materials with superior Zn ion storage performance. [ABSTRACT FROM AUTHOR]

Stable and efficient green hybrid light-emitting diodes (HLEDs) were fabricated from a highly emissive Mg(II)-tetraphenyl ethylene derivative metal–organic framework embedded in a polystyrene matrix (Mg-TBC MOF@PS). The photoluminescence quantum yield (φ) of the material, >80%, remains constant upon polymer embedment. The resulting HLEDs featured high luminous efficiencies of >50 lm W−1 and long lifetimes of >380 h, making them among the most stable MOF-based HLEDs. The significance of this work relies on the combination of many features, such as the abundance of the metal ion, the straightforward scalability of the synthetic protocol, the great φ reached upon phosphor fabrication, and the state-of-the-art HLED performances. [ABSTRACT FROM AUTHOR]

This study presents a new method for detecting and monitoring heavy metal ions in water samples. The method uses liquid crystal‐based optical sensors and a molecular probe called dodecyl‐N‐iminodiacetic acid (DIDAA). The probe's hydrophilic polar diacetate head group acts as a chelator for heavy metal ions, while its hydrophobic non‐polar tail aligns the liquid crystal molecules. When heavy metal ion‐contaminated water samples are introduced, the LC alignment is rapidly disrupted, resulting in bright optical signals. The sensor has a detection limit of 0.1, 0.3, 1.0, and 5.0 μM for for Mercury (Hg2+), Copper (Cu2+), Cadmium (Cd2+), and Lead (Pb2+) respectively. The diacetate probe remains effective even after multiple uses and was not affected by changes in pH. Its activity could persist for over 5 days. Furthermore, this sensor could be reversed and reused to detect HMIs in the presence of EDTA, making it a potential candidate for developing logic gates at the molecular level. [ABSTRACT FROM AUTHOR]

Multi‐excitonic emitting materials in luminescent metal halides are emerging candidates for anti‐counterfeiting and information encryption applications. Herein, ATPP2SnCl6 (ATPP=acetonyltriphenylphosphonium) phase was designed and synthesized by rationally choosing emissive organic reagent of ATPPCl and non‐toxic stable metal ions of Sn4+, and Sb3+ was further doped into ATPP2SnCl6 to tune the photoluminescence with external self‐trapped excitons emission. The derived non‐toxic ATPP2SnCl6 shows multi‐excitonic luminescent centers verified by optical study and differential charge‐density from density functional theory calculations. Incorporation of Sb3+ dopants and the increasing concentrations induce the efficient energy transfer therein, thus enhancing photoluminescence quantum yield from 5.1 % to 73.8 %. The multi‐excitonic emission inspires the creation of information encryption and decryption by leveraging the photoluminescence from ATPPCl to ATPP2SnCl6 host and ATPP2SnCl6 : Sb3+. This study facilitates the anti‐counterfeiting application by employing solution‐processable luminescent metal halides materials with excitation‐dependent PL properties. [ABSTRACT FROM AUTHOR]

The bonding effects between 3d transition‐metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition‐metal atoms of the spontaneous geometrical distortions, that is the Jahn–Teller effect, can alter CFSE, thereby leading to the Irving–Williams series. However, engineering single‐atom sites (SASs) using the Irving–Williams series as an ideal guideline has not been reported to date. Herein, alkynyl‐linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving–Williams series was employed to accurately predict the bonding effects between 3d transition‐metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu‐SASs/CPFs exhibits higher stability and faster charge‐transfer efficiency, far surpassing other metal‐SASs/CPFs. As expected, Cu‐SASs/CPFs demonstrates a high photoreduction of CO2‐to‐CO activity (~30.3 μmol ⋅ g−1 ⋅ h−1) and an exceptional photooxidation of CH3CHO‐to‐CH3COOH activity (~24.7 μmol ⋅ g−1 ⋅ h−1). Interestingly, the generated *O2− is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving–Williams to regulate the catalytic performances. [ABSTRACT FROM AUTHOR]

We report a series of coordination cages that incorporate peptide chains at their vertices, prepared through subcomponent self‐assembly. Three distinct heterochiral tripeptide subcomponents were incorporated, each exhibiting an L−D−L stereoconfiguration. Through this approach, we prepared and characterized three tetrahedral metal‐peptide cages that incorporate thiol and methylthio groups. The gelation of these cages was probed through the binding of additional metal ions, with the metal‐peptide cages acting as junctions, owing to the presence of sulfur atoms on the peripheral peptides. Gels were obtained with cages bearing cysteine at the C‐terminus. Our strategy for developing functional metal‐coordinated supramolecular gels with a modular design may result in the development of materials useful for chemical separations or drug delivery. [ABSTRACT FROM AUTHOR]

Multi‐excitonic emitting materials in luminescent metal halides are emerging candidates for anti‐counterfeiting and information encryption applications. Herein, ATPP2SnCl6 (ATPP=acetonyltriphenylphosphonium) phase was designed and synthesized by rationally choosing emissive organic reagent of ATPPCl and non‐toxic stable metal ions of Sn4+, and Sb3+ was further doped into ATPP2SnCl6 to tune the photoluminescence with external self‐trapped excitons emission. The derived non‐toxic ATPP2SnCl6 shows multi‐excitonic luminescent centers verified by optical study and differential charge‐density from density functional theory calculations. Incorporation of Sb3+ dopants and the increasing concentrations induce the efficient energy transfer therein, thus enhancing photoluminescence quantum yield from 5.1 % to 73.8 %. The multi‐excitonic emission inspires the creation of information encryption and decryption by leveraging the photoluminescence from ATPPCl to ATPP2SnCl6 host and ATPP2SnCl6 : Sb3+. This study facilitates the anti‐counterfeiting application by employing solution‐processable luminescent metal halides materials with excitation‐dependent PL properties. [ABSTRACT FROM AUTHOR]

The bonding effects between 3d transition‐metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition‐metal atoms of the spontaneous geometrical distortions, that is the Jahn–Teller effect, can alter CFSE, thereby leading to the Irving–Williams series. However, engineering single‐atom sites (SASs) using the Irving–Williams series as an ideal guideline has not been reported to date. Herein, alkynyl‐linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving–Williams series was employed to accurately predict the bonding effects between 3d transition‐metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu‐SASs/CPFs exhibits higher stability and faster charge‐transfer efficiency, far surpassing other metal‐SASs/CPFs. As expected, Cu‐SASs/CPFs demonstrates a high photoreduction of CO2‐to‐CO activity (~30.3 μmol ⋅ g−1 ⋅ h−1) and an exceptional photooxidation of CH3CHO‐to‐CH3COOH activity (~24.7 μmol ⋅ g−1 ⋅ h−1). Interestingly, the generated *O2− is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving–Williams to regulate the catalytic performances. [ABSTRACT FROM AUTHOR]

We report a series of coordination cages that incorporate peptide chains at their vertices, prepared through subcomponent self‐assembly. Three distinct heterochiral tripeptide subcomponents were incorporated, each exhibiting an L−D−L stereoconfiguration. Through this approach, we prepared and characterized three tetrahedral metal‐peptide cages that incorporate thiol and methylthio groups. The gelation of these cages was probed through the binding of additional metal ions, with the metal‐peptide cages acting as junctions, owing to the presence of sulfur atoms on the peripheral peptides. Gels were obtained with cages bearing cysteine at the C‐terminus. Our strategy for developing functional metal‐coordinated supramolecular gels with a modular design may result in the development of materials useful for chemical separations or drug delivery. [ABSTRACT FROM AUTHOR]

Water pollution with heavy metals owing to industrial and agricultural activities have become a critical dilemma to humans, plants as well as the marine environment. Therefore, it is of great importance that the carcinogenic heavy metals present in wastewater to be eliminated through designing treatment technologies that can remove multiple pollutants. A novel green magnetic nano-composite called (Carbonized Chitosan-Fe3O4-SiO2) was synthesized using Co-precipitation method to adsorb a mixture of heavy metal ions included; cobalt (Co2+), nickel (Ni2+) and copper (Cu2+) ions from aqueous solutions. The novelty of this study was the synthesis of a new nano-composite which was green with magnetic properties to be more sustainable and environmentally friendly. Its magnetic properties made it separated easily from solutions after accomplishment of the adsorption process using a magnet. Extended Freundlich isotherm was the best fitted model with maximum adsorption capacity of the metal ions mixture 2908.92 mg/g. Different experimental parameters have been studied included the initial concentration for a mixture of nickel, cobalt and copper metal ions (0.05–0.1 molar), dosage of adsorbent (0.5–3.5 g/L) and contact time (6–90 min) to investigate their changing effect on the removal percents of the heavy metal ions mixture from aqueous solutions. The experimental adsorption percent of cobalt ion ranged from 1.58 to 64.28%, nickel ion adsorption percent ranged from 10.68 to 94.12% and copper ion adsorption percent ranged from 4.41 to 76.23% at pH = 9 were based on the combination of the adsorption process parameters. [ABSTRACT FROM AUTHOR]

With the objective of gaining insight into the modulation of the reduction potential of the Ni(II / I) couple, we have synthesized two mononuclear nickel(II) complexes, NiLen (H2Len = N,N′-bis(3-methoxysalicylidene)-1,2-diamino-2-methylpropane) and NiLpn (H2Lpn = N,N′-bis(3-methoxysalicylidene)-1,3-diamino-2,2-dimethylpropane) of two N2O4 donor ligands and recorded their cyclic voltammograms. Both the nickel complexes show reversible reduction processes for the Ni(II / I) couple in acetonitrile solution but the reduction potential of NiLpn (E1/2 = −1.883 V) is 188 mV more positive than that of NiLen (E1/2 = −2.071 V). In the presence of redox inactive metal ions (Li+, Na+, K+, Mg2+, Ca2+ and Ba2+), the reduction potentials are shifted by 49–331 mV and 99–435 mV towards positive values compared to NiLen and NiLpn, respectively. The shift increases with the decrease of the pKa of the respective aqua-complexes of the metal ion but is poorly co-linear; however, better linearity is found when the shift of the mono- and bi-positive metal ion aqua complexes is plotted separately. Spectrophotometric titrations of these two nickel complexes with the guest metal ions in acetonitrile showed a well-anchored isosbestic point in all cases, confirming the adduct formation of NiLen and NiLpn with the metal ions. Structural analysis of single crystals, [(NiLen)Li(H2O)2]·ClO4 (1), [(NiLpn)Li(H2O)]·ClO4 (2), [(NiLpn)2Na]·BF4 (3) and [(NiLpn)2Ba(H2O)(ClO4)]·ClO4 (4), also corroborates the heterometallic adduct formation. The orbital energies of the optimised heterometallic adducts from which electron transfers originated were calculated in order to explain the observed reduction process. A strong linear connection between the calculated orbital energies and the experimental E1/2 values was observed. According to MEP and 2D vector field plots, the largest shift for divalent metal ions is most likely caused by the local electric field that they impose in addition to Lewis acidity. [ABSTRACT FROM AUTHOR]

Removing heavy metal (loid) s (HMs) from contaminated soil in a nonselective, highly efficient, and energy‐free manner is a major global challenge. Herein, this work synthesizes and assembles a biomimetic materials system (BMS) consisting of an artificial plant, a hemispherical glass cover, and a reflective plate, capable of non‐selective and highly efficient remediation of soil contaminated by various HM ions under sunlight. Specifically, a water cycle is driven to establish between the soil, artificial plant, and atmosphere by solar energy in the BMS, which induced water‐soluble HM ions to enrich and precipitate at the top edge of the artificial plant. The formed HM precipitate is easily removed, contributing to the extremely strong recyclability of BMS. This system has significant advantages in terms of soil properties, contamination characteristics, energy consumption, processing time, and removal amount over other representative remediation methods, demonstrating its great potential for practical application in the remediation of various HM‐contaminated soils. [ABSTRACT FROM AUTHOR]