Metal Interactions Research Articles

Porphyrin-Based Aluminum Metal-Organic Framework with Copper: Pre-Adsorption of Water Vapor, Dynamic and Static Sorption of Diethyl Sulfide Vapor, and Sorbent Regeneration

Metal–organic frameworks (MOFs) are hybrid inorganic–organic 3D coordination polymers with metal sites and organic linkers, which are a “hot” topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal–organic framework (actAl-MOF-TCPPCu) compound 4 with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound 4 was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH2 compound 2 by inserting Cu2+ ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound 4 with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent–adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO−, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound 4 at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)1.0(H2O)8.0. The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)1.0(H2O)8.0(DES)3.8 was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound 4). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound 4 and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air.

Effect of silane-doped argon shielding gases for gas metal arc welding of S355

The welding of steel grades relies primarily on the interaction of the weld metal with doped oxygen components of the shielding gas. This mainly serves to decrease the viscosity and reduce the surface tension of the melt in order to achieve an adjusted material transition. Interference with the ambient atmosphere is undesirable in this context. In order to prevent material-related changes in the microstructure, slag initiators are admixed which promote the precipitation of low-density oxides on the weld seam surface. Manufacturing technology is increasingly striving to eliminate the interaction of atmospheric oxygen in the production process. It is primarily intended to counteract the negative effects of oxygen during manufacturing. For this objective, silane-doped gases for subtractive manufacturing processes and additive manufacturing via the PBF-LB/M process have been considered. Small amounts of silane in conventional inert shielding gases allow partial pressures of oxygen that are comparable to a high vacuum. In the scope of this publication on investigations for welding applications, blind welds on S355 substrate plates were performed using G3Si1 filler material. In addition to the recommended M21, an argon shielding gas with 1.5% silane doping and argon 4.6 are applied for welding. Apart from the observation of the resulting energy input, the weld seams are metallographically characterized. For this purpose, the formation of silicates on the weld seam surface and the development of the weld seam within the base material are investigated. The volume of the weld seam is reduced as a result of the silane doping compared to the M21 application. The composition of the weld metal is significantly influenced by the silane content, leading to an increased manganese content in particular. The silane doping results in an intensified formation of an acicular bainitic structure and an accompanying hardening within the weld metal.

High–Field EPR Studies on Three Binuclear μ–Oxo–Bridged Iron(III) Complexes: Na4[Fe(edta)]2O ⋅ 3H2O, [Fe(phen)2(H2O)]2O(NO3)4 ⋅ 5H2O and [Fe(salen)]2O

AbstractA High–Field, High–Frequency Electron Paramagnetic Resonance (HFEPR) study was performed on the binuclear μ–oxo bridged complexes Na4[Fe(edta)]2O ⋅ 3H2O, [Fe(phen)2(H2O)]2O(NO3)4 ⋅ 5H2O and [Fe(salen)]2O, where edtaH4 = ethylenediaminetetraacetic acid, phen=1,10–phenanthroline and salenH2 is NN′–ethylenebis(salicylideneimine). The spin Hamiltonian parameters were determined for the thermally excited spin states with spin S=1, 2 and 3. The contributions to the zero–field splitting due to the local zero field splitting on individual iron ions and to the anisotropic metal–metal interactions were evaluated. Surprisingly large magnitudes of the anisotropic exchange interactions were found.

A New Model for Describing the Glass to Metal Interaction in Forming

A New Model for Describing the Glass to Metal Interaction in Forming

High-Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates-Stabilized *CO Intermediate.

Stabilizing specific intermediates to produce CH4 remains a main challenge in solar-driven CO2 reduction. Herein, g-C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x=12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80 % and 40.8 μmol ⋅ g-1 ⋅ h-1 evolution rate for PW9/g-C3N4. Conversely, g-C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g-C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g-C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g-C3N4 (x=12, 11) compared with that of PW9/g-C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

High‐Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates‐Stabilized *CO Intermediate

AbstractStabilizing specific intermediates to produce CH4 remains a main challenge in solar‐driven CO2 reduction. Herein, g‐C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x=12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80 % and 40.8 μmol ⋅ g−1 ⋅ h−1 evolution rate for PW9/g‐C3N4. Conversely, g‐C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g‐C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g‐C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g‐C3N4 (x=12, 11) compared with that of PW9/g‐C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

Boosting bio-lipids hydrodeoxygenation via highly dispersed and coking-resistance bimetallic Ni-La/SiO2 catalyst

A highly dispersed and coking-resistance bimetallic Ni-La/SiO2 catalyst was prepared for the selective hydrodeoxygenation (HDO) of fatty acid methyl esters (FAMEs) and non-edible bio-lipids to hydrocarbon compounds. Under optimum conditions, full conversion of methyl palmitate (MP) and 97.6% selectivity for pentadecane (PD) were achieved. The catalyst also exhibited high conversion and excellent desired product selectivity for the HDO of various model FAMEs, fatty acids, trilaurin, jatropha oil (JO) and waste cooking oil (WCO). Multiple characterizations show that the embedding effect (metal−support or metal−metal interaction) associated with the introduction of metallic La not only contributes to the formation of well-dispersed Ni particles and abundant active Niδ+−OV−LaOx species, but also prevents the migration and sintering of metallic Ni particles at high temperatures. Furthermore, the mutual transformation of the La2O3 and La2O2CO3 crystal phases effectively inhibits coke deposition on the catalyst surface during the reaction process, resulting in remarkable stability and reusability of the catalyst. A plausible reaction network and mechanism for the catalytic HDO of MP over Ni-La/SiO2 catalyst were proposed. This method of constructing a catalytic system can provide a basis for the development of efficient catalysts for the HDO of non-edible bio-lipids.

Enhanced anticancer and biological activities of environmentally friendly Ni/Cu-ZnO solid solution nanoparticles

The study investigates the impact of incorporating Ni and Cu into the lattice of ZnO nanoparticles (NPs) to enhance their anticancer and antioxidant properties. Characterization techniques including pXRD, FTIR, UV–visible absorption spectroscopy, FESEM, and EDAX confirm the successful synthesis and structural modifications of Ni/Cu-ZnO NPs. Anticancer activity against breast cancer (MDA) and normal skin (BHK-21) cells reveals dose-dependent cytotoxicity, with Ni/Cu-ZnO NPs exhibiting higher efficacy against MDA cells while being less harmful to BHK-21 cells. Morphological studies corroborate these findings. Additionally, antioxidant assays using TAC, FRAP, and DPPH assay demonstrate the superior antioxidant activity of Ni/Cu-ZnO NPs matched to pure ZnO. Overall, the synergistic effect of Ni and Cu incorporation leads to improved therapeutic potential, making Ni/Cu-ZnO NPs promising candidates for cancer therapy and antioxidant applications.Molecular docking recreations were performed using Auto Dock Vina software to gain more insights and validate the observed biological activities of un-doped ZnO and bi-metal doped ZnO NPs, we investigated the interaction and binding affinities of pure ZnO and bimetallic metal co-doped ZnO for their antioxidant and anticancer studies. Ni/Cu-ZnO have shown good antioxidants and exhibited remarkable anticancer activities.

Arsenic Stress Mitigation Using a Novel Plant Growth-Promoting Bacterial Strain Bacillus mycoides NR5 in Spinach Plant (Spinacia oleracea L.).

Present study aimed to identify arsenic (As)-resistant bacterial strains that can be used to mitigate arsenic stress. A bacterium Bacillus mycoides NR5 having As tolerance limit of 1100 mg L-1 was isolated from Nag River, Maharashtra, India. It was also equipped with plant growth-promoting (PGP) attributes like phosphate solubilization, siderophores, ammonia, and nitrate reduction, with added antibiotic tolerance. Furthermore, scanning electron microscopy (SEM) and transmission electron micrograph (TEM) suggested biosorption as possible mechanisms of arsenic tolerance. A strong peak in FTIR spectra at 3379.0 corresponding to amine in As-treated NR5 also indicated metal interaction with cell surface protein. Amplification of arsenic reductase gene in NR5 further suggested intracellular transformation of As speciation. Moreover, As tolerance capability of NR5 was shown in spinach plants in which the bacterium effectively mitigated 25 ppm As by producing defense-related proline molecules. Evidence from SEM, TEM, and FTIR, concluded biosorption possibly the primary mechanism of As tolerance in NR5 along with the transformation of arsenic. B. mycoides NR5 with PGP attributes, high As tolerance, and antibiotic resistance mediated enhanced As tolerance in spinach plants advocated that the strain can be a better choice for As bioremediation in contaminated agricultural soil and water.

Predicting potential hard materials in Nb[sbnd]B ternary boride: First-principles calculations

To identify potential superhard materials, we conducted a comprehensive theoretical investigation of the thermodynamic and kinetic stability, mechanical properties, electronic structure, Debye temperatures and melting point of sixteen ternary transition metal borides NbTMBx (x = 1, 2, 4 and TM = Ti, V, Fe, Co, Ni, Zr, Ru, Hf, W, Os) using first-principles methods. Our findings indicate that, with the exception of NbFeB, NbRuB, and NbWB, all other borides exhibit both thermodynamic and kinetic stability. Notably, NbTiB4, NbVB4, NbZrB4 and NbHfB4 demonstrate superior hardness and enhanced resistance to deformation, with NbTiB4 showing an impressive hardness value of 40.84 GPa, positioning it as a promising candidate for superhard materials. Both NbVB4 and NbTiB4 have very high Debye temperatures and melting points and can be used in high temperature environments. We further explored the mechanical properties of NbTiB4 at elevated temperatures by employing a combination of first-principles and quasi-static methods. Our analysis reveals that the elastic constants and moduli of NbTiB4 decrease with increasing temperature. Additionally, bonding analysis indicates that all NbB ternary borides exhibit hybridization involving metallic, ionic, and covalent interactions, resulting in the formation of exceptionally strong covalent bonds between boron atoms.

Long-term interaction of metals and phosphate with ferrihydrite in artificial seawater and implications for past and present environments

The FeIII hydroxide ferrihydrite (Fh) is highly reactive towards dissolved metals and other aqueous compounds. This reactivity suggests a possible role for Fh in environmental remediation and in controlling ambient concentrations of metals and nutrients in both modern and ancient aqueous environments. Though the reactivity of Fh towards a variety of aqueous compounds has been determined in previous studies, its reactivity under seawater-like conditions has not been systematically explored. Since solution chemistry can have a profound effect on the uptake of metals and oxyions through its effects on the surface chemistry of Fh and the speciation of metals in solution, the dearth of experiments under seawater-like conditions translates into a knowledge gap of metal-Fh interactions in natural marine systems. Furthermore, metal- and nutrient-Fh interactions have been investigated under dissimilar conditions, making a quantitative comparison of these interactions difficult. Lastly, the fate of the aqueous metals and nutrients taken up by Fh upon its aging has been examined in only a few studies and mostly for a duration up to ∼8 months.We bridged these gaps in a series of adsorption and co-precipitation experiments of various metals and phosphate with Fh, in seawater-analog solutions, at circumneutral pH (pH 7.5 and 8.0) and 25 °C. We quantified the effect of interaction with Fh on the aqueous concentrations of CdII, CoII, CrVI, CuII, MnII, MoVI, NiII, VV, UVI, ZnII, and phosphate (PO43−). The experimental results are provided as uptake percentages (quantified as the metal:Fe ratio in the solid phase relative to the metal:Fe ratio added) at different metal:Fe ratios and as a series of partition coefficients of the studied metals and PO43− between aqueous solution and Fh. Additionally, aging experiments of up to ∼4 years in duration were used to determine the potential effects of grain coarsening, surface modification and mineral transformation on the uptake of the metals and PO43−. Uptake of CrVI, MoVI and UVI was negligible in both the adsorption and co-precipitation experiments. Uptake of VV and PO43− by co-precipitation was as much as twice their uptake by adsorption, and we suggest that stabilization of colloidal Fh with a large surface area explains these findings. For CuII, NiII, CoII, MnII, and CdII differences in uptake between the co-precipitation and adsorption experiments were less pronounced, and we ascribe these differences to relatively minor incorporation of these metals into Fh. No significant transformation of Fh to more stable phases was observed under our experimental conditions and duration. Nevertheless, the uptake of several metals and phosphate was affected by Fh aging. Approximately 75% of the PO43− initially taken up by co-precipitation with Fh was released, as was approximately 30% of the VV. A pronounced increase in the uptake of MnII may be related to its oxidation and precipitation as MnIII,IV oxides. For other metals the changes in uptake were less pronounced.We discuss the mechanisms of metal and PO43− uptake by Fh, the effects of solution composition on uptake, and the implications of our findings for modern and ancient natural environments and for environmental remediation.

An Evaluation of Metal Binding Constants to Cell Surface Receptors in Freshwater Organisms, and Their Application in Biotic Ligand Models to Predict Metal Toxicity

Biotic ligand models (BLMs) predict the toxicity of metals in aquatic environments by accounting for metal interactions with cell surface receptors (biotic ligands) in organisms, including water chemistry (metal speciation) and competing cations. Metal binding constants (log KMBL values), which indicate the affinity of metals for cell surface receptors, are fundamental to BLMs, but have only been reported for a few commonly investigated metals and freshwater species. This review evaluated literature toxicity and uptake data for seven key metals (cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), uranium (U), and zinc (Zn)) and four key competing cations (protons (H), calcium (Ca), magnesium (Mg), and sodium (Na)), to derive average metal binding constants for freshwater organisms/taxa. These constants will improve current BLMs for Cd, Cu, Ni, Pb, and Zn, and aid in developing new BLMs for Co and U. The derived metal binding constants accurately predicted metal toxicity for a wide range of freshwater organisms (75–88% of data were within a factor of two and 88–98% of data were within a factor of three of the ideal 1:1 agreement line), when considering metal speciation, competing cations and the fraction of cell receptors ((fC)M50%) occupied by the metal at the median (50%) effect concentration (EC50). For many organisms, toxicity occurs when 50% of cell surface receptors are occupied by the metal, though this threshold can vary. Some organisms exhibit toxicity with less than 50% receptor occupancy, while others with protective mechanisms show reduced toxicity, even with similar log KMBL values. For Cu, U, and Pb, the toxic effect of the metal hydroxide (as MOH+) must be considered in addition to the free metal ion (M2+), as these metals hydrolyse in circumneutral freshwaters (pH 5.5 to 8.5), contributing to toxicity.

Physical and chemical characteristics and activity of nickel-modified cobalt-iron-containing catalysts in the reaction of dry reforming of methane

In the process of dry reforming of methane (DRM), the activity of low-percentage catalysts based on cobalt and iron oxides and their modification with nickel oxide was studied. It has been established that the addition of nickel oxide into the Fe2O3/γ-Al2O3 catalyst increases the degree of methane conversion from 14 to 89%, and also increases the yield of target reaction products H2 to 43.0 vol.%, CO to 46.1 vol.% at 850 °C. On a Co3О4-NiО/γ-Al2O3 catalyst at 850 °C, methane conversion reaches to 88.1%, the yield of H2 and CO is 44.8%. TPR-H2 analyzes showed that the introduction of nickel oxide into Fe2O3/γ-Al2O3 composition, in contrast to the Co3O4/γ-Al2O3 catalyst, the temperature peaks of Fe2O3-NiО/γ-Al2O3, reduction shift towards lower temperatures and weaken the interaction of metals with the support - γ-Al2O3 and thereby the amount of active reduced particles of iron and nickel oxides increases, which ensures good catalytic activity of Fe2O3-NiО/γ-Al2O3. According to the XRD results, spinel-like form - NiFe2O4, NiAl2O4 and CoAl2O4, also phase as Fe2O3 were obtained on the Fe2O3-NiО/γ-Al2O3 catalyst. This indicates that the developed catalysts form new phases that are active at high temperatures to produce synthesis gas in reduction-oxidation processes during the DRM reaction.

Unraveling Oxygen Vacancies Effect on Chemical Composition, Electronic Structure and Optical Properties of Eu Doped SnO2.

The influence of Eu doping (0.5, 1 and 2 mol.%) and annealing in an oxygen-deficient atmosphere on the structure and optical properties of SnO2 nanoparticles were investigated in relation to electronic structure. The X-ray diffraction (XRD) patterns revealed single-phase tetragonal rutile structure for both synthesized and annealed Eu-doped SnO2 samples, except for the annealed sample with 2 mol.% Eu. The results of X-ray photoelectron spectroscopy (XPS) emphasized that europium incorporated into the SnO2 host lattice with an oxidation state of 3+, which was accompanied by the formation of oxygen vacancies under cation substitution of tetravalent Sn. Moreover, XPS spectra showed the O/Sn ratio, which has been reduced under annealing for creating additional oxygen vacancies. The pulse cathodoluminescence (PCL) demonstrated the concentration dependence of Eu site symmetry. Combination of XRD, XPS and PCL revealed that Eu doping and following annealing induce strongly disordering of the SnO2 crystal lattice. Our findings provide new insight into the interaction of rare-earth metals (Eu) with host SnO2 matrix and new evidence for the importance of oxygen vacancies for optical and electronic structure formation.

Effect of transition and alkali metals on Mo2C/Al2O3 catalysts for syngas to higher alcohols

Direct production of higher alcohols remains a great challenge in syngas conversion process. Herein, MMo2C/Al2O3 and KMMo2C/Al2O3 catalysts promoted by different transition metals M (M=Co, Fe, Cu, Ni, Zn, Nb) and alkali metal (K) were prepared by impregnation method to investigate the effect on CO hydrogenation to higher alcohols under milder reaction conditions (300°C, 3.0 MPa). The catalysts were characterized with XRD, H2-TPR, and XPS. It was found that the addition of transition metals and K resulted in the decrease of low-valent Mo species on the catalyst surface, which facilitated the generation of Mo4+ during the reaction. Increase in Mo4+ content facilitates the conversion of CO to CO*, which provides more CO insertion sites for the generation of alcohols. Moreover, the introduction of K also enhances the interaction of transition metals with Mo, which accelerates the formation of alcohols in the reaction. Meanwhile, the transition metal and Mo2C work together to promote the dissociative adsorption of CO. The production of higher alcohols is facilitated by the synergistic effect of the two mentioned above. Overall, the KCoMo/Al2O3 and KFeMo/Al2O3 catalysts exhibited high selectivity for higher alcohols, reaching 73.9 % and 71.3 % for C2+OH in the alcohol products, respectively. CO conversion of KFeMo/Al2O3 catalyst can reach 84.9 % with excellent stability in the reaction. Moreover, the possible pathways of the reaction were obtained by in-situ DRIFT characterization.

Temperature measurement in laser–metal processing using optical sensing: Radiometric calibration and validation of a multispectral camera

In laser–metal processing such as Laser-based Powder Bed Fusion of Metals (PBF-LB/M), the quality of the final product is significantly influenced by the thermal behaviour of the melt pool. Accurate temperature measurements are challenging due to high temperature gradients and rapid cooling. This study introduces Multispectral Imaging (MSI) as a highly effective thermometry technique to address these demanding conditions. MSI captures multiple bands of radiation, enabling the simultaneous determination of absolute temperature and surface emissivity. This capability is crucial for ensuring high-quality outcomes in laser–metal processing such as PBF-LB/M, contingent upon robust radiometric calibration.To enhance reliability, two radiometric calibration models were developed: an empirical model based on linear sensor data correlations and an analytical model leveraging sensor behaviour. An efficient calibration was found for both models across a range of signal-to-noise ratios in the black body calibrator, where the analytical model even performs robust under a high noise level.Additionally, the temperature accuracy in the solid-state case was tested with a thermo-mechanical simulator. Results showed that the empirical and analytical models achieved mean relative errors of 2.0% and 1.6%, respectively, outperforming the state-of-the-art. Further, laser irradiation experiments highlighted the analytical model’s ability to accurately determine the emissivity decrease during the solid-to-liquid transition, allowing for accurate melt pool temperature estimations. Conversely, the empirical model struggled to estimate temperature effectively in the liquid phase.This study not only proposed a robust methodology of MSI in temperature measurement but also confirmed the accuracy and reliability of the system, broadening the scope for further investigation into the intricate thermal dynamics involved in laser–metal interactions.

The emerging application of LC-based metallomics techniques to unravel the bioinorganic chemistry of toxic metal(loid)s

The on-going anthropogenic emission of toxic metal(loid) species into the environment contaminates the food supply and drinking water resources in various parts of the world. Given that inorganic pollutants cannot be degraded, their increased influx into the bloodstream of babies, children and pregnant women is inevitable. Since the ramifications of the ensuing environmental exposure on human health remain poorly defined, fundamentally new insight into their bioinorganic chemistry in organisms is urgently needed. Based on the flow of dietary constituents through organisms, the interaction of toxic metal(loid) species with biomolecules in the bloodstream deserve particular attention as they play an integral role in the mechanisms of their chronic toxicity. Gaining insight into these bioinorganic processes is hampered by the biological complexity of plasma/red blood cells and the low concentrations of the metal(loid) species of interest, but can be overcome by employing LC techniques hyphenated to atomic spectroscopic detectors (i.e. metallomics techniques). This perspective aims to highlight the potential of unconventional hyphenated separation modes to advance our understanding of the bioinorganic chemistry of toxic metal(loid) species in the bloodstream-organ system. Four examples are illustrated. The application of anion-exchange (AEX) and size-exclusion chromatography (SEC) provided new insight into the blood-based bioinorganic mechanisms that direct Cd2+ and MeHg+ to target organs. AEX chromatography also allowed to observe the formation of complexes between Hg2+ and MeHg+ with L-cysteine at pH 7.4, that are implicated in their organ uptake. Lastly, the application of reversed phase (RP) chromatography revealed a possible cytosolic mechanism by which N-acetyl-L-cysteine binds to MeHg+ in the presence of cytosolic glutathione (GSH). New insight into other bioinorganic processes may advance the regulatory framework to better protect public health.

Intrinsic Electron Transfer in Heteronuclear Dual‐Atom Sites Facilitates Selective Electrocatalytic Carbon Dioxide Reduction

AbstractThe metal–metal (M1–M2) interactions in heteronuclear dual‐atom catalysts (HNDACs) significantly optimize the electronic properties of the active sites, resulting in the promotion of the reaction kinetics in electrocatalysis. However, the regulation mechanisms in these M1–M2 dual‐atom sites still remain unclear. Herein, the intrinsic electron transfer in Fe–Zn dual‐atom sites are revealed for facilitating electrocatalytic carbon dioxide reduction (ECO2R) to carbon monoxide (CO). The electronegativity difference between the Fe and Zn centers induces the specific electron transfer from Zn to Fe, which regulates the electron structures of the active Zn sites, leading to the optimized reaction pathway of CO2‐to‐CO conversion on these sites. The Fe–Zn HNDAC (FeZnNC) exhibits superior ECO2R performances than the single‐atom Fe/Zn catalysts (FeNC and ZnNC) in the typical H‐cell system, the maximum CO partial current density on FeZnNC reaches more than 3.3 and 1.8 folds of those on FeNC and ZnNC, respectively. More importantly, in a strongly acidic medium (pH = 1), FeZnNC achieves CO Faradaic efficiencies greater than 94% in the current density range of 100–400 mA cm−2. This work uncovers the intrinsic electron transfer at the heteronuclear diatomic sites, providing new insights for the rational design of high‐performance HNDACs toward industrial electrocatalysis.

Catalysis on Mono- and Bimetallic Nanoparticles of the Silver–Copper System Cu<sub><i>n</i></sub>Ag<sub><i>m</i></sub>

The purpose of this work is to study the catalytic properties of mono- and bimetallic nanoparticles of the copper-silver system of variable composition supported on aluminum oxide in the conversion reactions of protium modifications and deuterium-hydrogen exchange. From a comparison of the temperature dependences of the specific catalytic activity of the samples in the two reactions under study, a conclusion was drawn about different reaction mechanisms. It has been shown that, compared to bulk metals, nanoparticles of the CunAgm composition have catalytic properties in a wide temperature range, up to 77 K. In the chemical reaction of isotope exchange in molecular hydrogen, a synergistic effect is observed, which indicates the interaction of metals in biparticles.

ATH434, a promising iron-targeting compound for treating iron regulation disorders.

Cytotoxic accumulation of loosely bound mitochondrial Fe2+ is a hallmark of Friedreich's Ataxia (FA), a rare and fatal neuromuscular disorder with limited therapeutic options. There are no clinically approved medications targeting excess Fe2+ associated with FA or the neurological disorders Parkinson's disease and Multiple System Atrophy. Traditional iron-chelating drugs clinically approved for systemic iron overload that target ferritin-stored Fe3+ for urinary excretion demonstrated limited efficacy in FA and exacerbated ataxia. Poor treatment outcomes reflect inadequate binding to excess toxic Fe2+ or exceptionally high affinities (i.e. ≤10-31) for non-pathologic Fe3+ that disrupts intrinsic iron homeostasis. To understand previous treatment failures and identify beneficial factors for Fe2+-targeted therapeutics, we compared traditional Fe3+ chelators deferiprone (DFP) and deferasirox (DFX) with additional iron-binding compounds including ATH434, DMOG, and IOX3. ATH434 and DFX had moderate Fe2+ binding affinities (Kd's of 1-4 µM), similar to endogenous iron chaperones, while the remaining had weaker divalent metal interactions. These compounds had low/moderate affinities for Fe3+(0.46-9.59µM) relative to DFX and DFP. While all compounds coordinated iron using molecular oxygen and/or nitrogen ligands, thermodynamic analyses suggest ATH434 completes Fe2+ coordination using H2O. ATH434 significantly stabilized bound Fe2+ from ligand-induced autooxidation, reducing reactive oxygen species (ROS) production, whereas DFP and DFX promoted production. The comparable affinity of ATH434 for Fe2+ and Fe3+ position it to sequester excess Fe2+ and facilitate drug-to-protein iron metal exchange, mimicking natural endogenous iron binding proteins, at a reduced risk of autooxidation-induced ROS generation or perturbation of cellular iron stores.