Search Results (71)

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies. Full article

This study synthesized two eco-friendly inhibitors—a chitosan–copper metal–organic framework (CS@Cu MOF) and chitosan–Schiff base–Cu complex (Schiff–CS@Cu)—for Q345 steel protection in 3.5% NaCl/1M HCl. Electrochemical and weight loss analyses demonstrated exceptional corrosion inhibition: untreated specimens showed a 25.889 g/(m²·h) corrosion rate, while 100 mg/L of CS@Cu MOF and Schiff–CS@Cu reduced rates to 2.50 g/(m²·h) (90.34% efficiency) and 1.67 g/(m²·h) (93.56%), respectively. Schiff–CS@Cu’s superiority stemmed from its pyridine–Cu²⁺ chelation forming a dense coordination barrier that impeded Cl⁻/H⁺ penetration, whereas CS@Cu MOF relied on physical adsorption and micro-galvanic interactions. Surface characterization revealed that Schiff–CS@Cu suppressed pitting nucleation through chemical coordination, contrasting with CS@Cu MOF’s porous film delaying uniform corrosion. Both inhibitors achieved optimal performance at 100 mg/L concentration. This work establishes a molecular design strategy for green inhibitors, combining metal–organic coordination chemistry with biopolymer modification, offering practical solutions for marine infrastructure and acid-processing equipment protection. Full article

The coordination chemistry, structural characterization, and biomolecular interactions of europium(III) and iron(III) complexes with the pyridoxal-semicarbazone (PLSC) ligand were thoroughly examined using experimental and computational approaches. Single-crystal X-ray diffraction revealed that the europium complex exhibits a nine-coordinate geometry with one protonated and one deprotonated PLSC ligand and nitrato and aqua ligands. In contrast, the iron complex adopts a six-coordinate structure featuring a monoprotonated PLSC, two chlorido, and an aqua ligand. Hirshfeld surface analysis confirmed the significance of intermolecular contacts in stabilizing the crystal lattice. Theoretical geometry optimizations using DFT methods demonstrated excellent agreement with experimental bond lengths and angles, thereby validating the reliability of the chosen computational levels for subsequent quantum chemical analyses. Quantum Theory of Atoms in Molecules (QTAIM) analysis was employed to investigate the nature of metal–ligand interactions, with variations based on the identity of the donor atom and the ligand’s protonation state. The biological potential of the complexes was evaluated through spectrofluorimetric titration and molecular docking. Eu-PLSC displayed stronger binding to human serum albumin (HSA), while Fe-PLSC showed higher affinity for calf thymus DNA (CT-DNA), driven by intercalation. Thermodynamic data confirmed spontaneous and enthalpy-driven interactions. These findings support using PLSC-based metal complexes as promising candidates for future biomedical applications, particularly in drug delivery and DNA targeting. Full article

The novel pyridine oxime-based complexing agents 2-pyridinecarboxaldehyde oxime, 2-acetylpyridine ketoxime and 2-pyridine amidoxime were synthesized for alkaline Zn-Ni alloy electrodeposition, outperforming conventional citrate/TEPA systems in corrosion resistance and microstructural control. The N,O-bidentate chelation mechanism governs metal ion reduction kinetics via diffusion-limited pathways, enabling γ-phase Ni₅Zn₂₁ intermetallic formation and nanocrystalline refinement. Electrochemical and microstructural analyses demonstrate suppressed random nucleation and hydrogen evolution side reactions, leading to enhanced charge transfer resistance and reduced corrosion current density. Notably, 2-pyridine amidoxime achieves ultrasmooth surfaces through defect-free nanocluster growth, while 2-pyridinecarboxaldehyde oxime maximizes γ-phase crystallinity. The synergy between grain boundary density and surface integrity establishes a dual protection mechanism combining barrier layer formation and active dissolution suppression. This work advances microstructure engineering via coordination chemistry, offering a breakthrough over traditional zincate electroplating for high-performance anti-corrosion coatings. Full article

Ternary metal chalcogenide quantum dots (QDs), such as CuInS₂, have attracted significant attention due to their lower toxicity compared to binary counterparts containing cadmium or lead, making them promising candidates for biomedical imaging and solar energy applications. The surfactant choice is critical for controlling nanocrystal nucleation, growth kinetics, and functionalization. This directly affects the toxicity and applications of QDs. In this work, we report a synthesis protocol for PVP-capped CuInS₂ QDs in an aqueous solution. Using density functional theory (DFT) calculations, we predicted the coordination patterns of PVP on the CuInS₂ QDs surface, providing insights into the stabilization mechanism. The synthesized QDs were characterized using TEM, XRD, XPS, and FTIR to assess their morphology, chemical composition, and surface chemistry. The QDs exhibited dual photoluminescence (PL) maxima at 550 nm and 680 nm, attributed to defect-related emissions, making them suitable for cell imaging applications. Cytotoxicity studies and cell imaging experiments demonstrate the excellent biocompatibility and effective staining capabilities of the PVP-capped CuInS₂ QDs, highlighting their potential as fluorescent probes for long-term, multicolor cell imaging including two-photon microscopy. Full article

A new complex, tetrakis(1,10-phenanthroline)-bis(succinate)-(µ₂-oxo)-bis(iron(III)) nonahydrate, [Fe₂(Phen)₄(Succinate)₂(μ-O)](H₂O)₉, was synthesized using the slow evaporation method. This study provides a comprehensive characterization of this coordination compound, focusing on its structural, spectroscopic, and thermal properties, which are relevant for applications in catalysis, material science, and chemical engineering processes. Single-crystal X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared (FT-IR), ultraviolet-visible (UV-Vis) spectroscopy, and thermoanalytical analyses were employed to investigate the material properties. Intermolecular interactions were further explored through Hirshfeld surface analysis. XRD results revealed a monoclinic crystal system with the C2/c space group, lattice parameters: a = 12.7772(10) Å, b = 23.0786(15) Å, c = 18.9982(13) Å, β = 93.047(2)°, V = 5594.27(7) ų, and four formulas per unit cell (Z = 4). The crystal packing is stabilized by C–H⋯O, C–O⋯H, C–H⋯π, and π⋯π intermolecular interactions, as confirmed by vibrational spectroscopy. The heteroleptic coordination environment, combining weak- and strong-field ligands, results in a low-spin state with an estimated crystal field stabilization energy of −4.73 eV. Electronic properties indicate direct allowed transitions (γ = 2) with a maximum optical band gap of 2.66 eV, suggesting potential applications in optoelectronics and photochemical processes. Thermal analysis demonstrated good stability within the 25–136 °C range, with three main stages of thermal decomposition, highlighting its potential for use in high-temperature processes. These findings contribute to the understanding of Fe(III)-based complexes and their prospects in advanced material design, catalytic systems, and process optimization. Full article

The interaction of nitrate radicals (NO₃) with the air–water interface is a critical aspect of atmospheric chemistry, influencing processes such as secondary organic aerosol (SOA) formation, pollutant transformation, and nighttime oxidation. This study investigates the behavior of NO₃ radicals at the air–water interface and in bulk water environments through ab initio molecular dynamics simulations, directly comparing them with Cl and ClO radicals. Three distinct configurations of NO₃ in water droplets were analyzed: surface-parallel, surface-perpendicular, and bulk-phase. The results reveal environment-dependent dynamics, with surface-localized NO₃ radicals exhibiting fewer but more flexible hydrogen bonds compared to bulk-solvated radicals. Analysis of radial distribution functions, coordination numbers, and population distributions demonstrates that NO₃ radicals maintain distinct interfacial and bulk-phase preferences, with rapid equilibration in both environments. Electronic structure analysis shows significant modulation of spin density and molecular orbital distributions between surface and bulk environments. The comparative analysis with Cl and ClO radicals highlights how the unique planar geometry and delocalized π-system of NO₃ influence its hydration patterns and interfacial activity. These results offer fundamental molecular-level insights into NO₃ radical behavior at the air–water interface and in aqueous environments, enhancing our understanding of their role in heterogeneous atmospheric processes and nocturnal chemistry. Full article

Silver (Ag) is a precious and valuable metal, and it has many carrier minerals. Through LA-ICP-MS analysis, it was found that jamesonite not only contains lead (Pb) and antimony (Sb) as precious metals but also trace amounts of Ag. In practice, the flotation method is generally used to recover these metals. This paper employs density functional theory calculations to demonstrate that after Ag doping in jamesonite, the Ag atoms exist in the lattice channels of jamesonite, and they form strong covalent bonds with the S atoms, resulting in strong interactions. When Ag is doped in the channels, the adsorption of sodium diethyldithiocarbamate (DDTC) as a collector on the Ag-doped jamesonite surface is the strongest, while that of butyl xanthate is the weakest. The adsorption interactions on the Ag-doped jamesonite surface are also stronger than on pure jamesonite. Coordination chemistry studies reveal that Ag⁺ undergoes a transition from a d¹⁰ to a d⁹s¹ electronic configuration when incorporated into jamesonite, which increases its reactivity by generating unpaired electrons available for π-backbonding with collector molecules. Furthermore, owing to the high polarizability of Ag, the presence of Ag atoms alters the electronic environment of the surrounding Pb atoms, which enhances the π-backbonding interactions between the adsorbate reagent molecules and the Ag active sites. The research results are of great significance for the efficient recovery of Ag-containing jamesonite and provide a reference for the study of the properties of Ag-doped minerals. Full article

The incorporation of transition metal atoms into [Ge₉] clusters is a widely studied area of Zintl-cluster chemistry. Recently, it was shown that clusters comprising single transition metal atoms in the cluster surface show catalytic properties. Here, we present a synthetic approach to four new compounds comprising silylated Ge₉ clusters with organometallic ruthenium complexes. [η⁵-Ge₉Hyp₃]RuCp* (1), [η¹-Ge₉(Si^tBu₂H)₃]RuCp(PPh₃)₂ (2), and [Hyp₃Ge₉][RuCp(PPh₃)₂(MeCN)] (3b) (Cp = cyclopentadienyl, Cp* = pentamethylcyclopentadienyl, Hyp = Si(SiMe₃)₃, Ph = C₆H₅, ^tBu = tert-butyl) were characterized by means of NMR spectroscopy and single-crystal structure determination. In the case of 2, a new isomer with an approximated C_4v symmetric monocapped square antiprism of nine Ge atoms with an unexpected ligand arrangement comprising three ditertbutylsilane ligands attached to the open square was obtained. [Hyp₃Ge₉][RuCp(PPh₃)₂] (3a) was characterized via NMR spectroscopy and LIFDI mass spectrometry. Overall, we were able to show that the steric demand of the ligands Cp vs. Cp* and hypersilylchloride vs. ditertbutylsilane strongly influence the arrangement of the atoms and ligands on the cluster. In addition, the solvent also affects the cluster, as it appears that the ruthenium atom in 3a dissociates from the cluster surface upon acetonitrile coordination to form 3b. These results show that choosing the right synthetic tools and ligands makes a big difference in the outcome of the metalation reaction. Full article

Metal phenolic networks (MPNs) have attracted significant attention due to their environmentally benign nature, broad compatibility, and universal adhesive properties, making them highly effective for modifying adsorbent surfaces. These supramolecular complexes are formed through the coordination of metal ions with natural phenolic ligands, resulting in stable structures while retaining the active adsorption sites of the ligands, thereby enhancing the adsorption performance of unmodified substrates. Among various MPNs, metal ion gallic acid (GA) networks are particularly well-known for their exceptional stability, biological activity, and superior adsorption ability. This review offers a comprehensive examination of GA-based MPN adsorbents, focusing on their formation chemistry, characterization techniques, and applications. The coordination chemistry underlying the stability of GA–metal complexes is analyzed through equilibrium studies, which are critical for understanding the robustness of MPNs. The main analytical methods for assessing metal ligand interactions are discussed, along with additional characterization techniques for evaluating adsorbent properties. This review also explores various synthesis and performance enhancement strategies for GA-based MPN adsorbents, including stand-alone MPNs, MPN-mediated mesoporous materials, MPN-MOF composites, and MPN-coated substrates. By consolidating current advancements in MPN-based adsorbents and offering fundamental insights into their chemistry and characterization, this review serves as a valuable resource for researchers seeking to develop stable, functional metal-organic materials. It aims to drive innovation in sustainable and efficient adsorbent technologies for diverse environmental and industrial applications. Full article

Area-selective atomic layer deposition (AS-ALD) is a technique utilized for the fabrication of patterned thin films in the semiconductor industry due to its capability to produce uniform and conformal structures with control over thickness at the atomic scale level. In AS-ALD, surfaces are functionalized such that only specific locations exhibit ALD growth, thus leading to spatial selectivity. Self-assembled monolayers (SAMs) are commonly used as ALD inhibiting agents for AS-ALD. However, the choice of organic molecules as viable options for AS-ALD remains limited and the precise effects of ALD nucleation and exposure to ALD conditions on the structure of SAMs is yet to be fully understood. In this work, we investigate the potential of small molecule carboxylates as ALD inhibitors, namely benzoic acid and two of its derivatives, 4-trifluoromethyl benzoic acid (TBA), and 3,5-Bis (trifluoromethyl)benzoic acid (BTBA) and demonstrate that monolayers of all three molecules are viable options for applications in ALD blocking. We find that the fluorinated SAMs are better ALD inhibitors; however, this property arises not from the hydrophobicity but the coordination chemistry of the SAM. Using nanoscale infrared spectroscopy, we probe the buried monolayer interface to demonstrate that the distribution of carboxylate coordination states and their evolution is correlated with ALD growth, highlighting the importance of the interfacial chemistry in optimizing and assessing ALD inhibitors. Full article

Sphalerite flotation is generally achieved by copper activation followed by xanthate collection. This study aims to propose a design idea to find novel collectors from the perspective of molecular design and prove the theoretical feasibility that the collector can effectively recover sphalerite without copper activation. To address this, 30 compounds containing different structures of sulfur atoms and different neighboring atoms were designed based on coordination chemistry. Twelve potential collectors were screened, and their properties and interactions with a hydrated sphalerite (110) surface were evaluated. Compound 27 (C₂H₄S₂²⁻) showed the greatest reactivity, suggesting that the double-coordination structure of two sulfhydryl groups is an effective molecular structure for direct sphalerite flotation. The DFTB+ and MD results demonstrate that 1,2-butanedithiol (C₄H₁₀S₂), having a similar coordination structure to compound 27, has the potential to replace the traditional reagent scheme of sphalerite flotation. The strong reagent–surface interaction is attributed to the overlap of Zn 3d with S 3p orbitals, the most negative electrostatic potential, the relatively high E_HOMO and low average local ionization energy, and the eliminated steric hindrance effect. It is expected that this study can provide a design idea for the targeted design and development of novel reagents for complex sulfide ore flotation. Full article

Medicinal Inorganic Chemistry has provided oncology with metallodrugs for cancer treatment, including several promising candidate drugs. In particular, copper(II) coordination compounds with phenanthroline stand out as potential anticancer agents. In this work, we used Differential Scanning Calorimetry and Electron Spin Resonance to investigate the interaction of the copper phenanthroline complexes [Cu(phen)]²⁺ and [Cu(L-dipeptide)(phenanthroline) (L-dipeptide: L-Ala-Gly and L-Ala-Phe)) with model lipid membranes (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC, and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1′-rac-glycerol) sodium salt, DPPG). Our results showed that the complexes interact with the membrane models, fluidizing them. The [Cu(phen)]²⁺ presented a different localization than the free ligand phen. The dipeptide modulated the localization of the complex in the membrane and the modifications induced in the physicochemical properties of the lipid vesicles. A stronger interaction with DPPG anionic membranes was observed, which mimic membranes with negatively charged surfaces, as found on several tumor cells. Full article

The formation of barium sulfate scale is a persistent and formidable challenge across various industrial processes. In order to effectively mitigate this problem, this study proposed the development of an innovative azacrown ether-based macrocycle descaling agent. Using density functional theory, an in-depth analysis of the surface energy of different barium sulfate crystal facets was carried out, together with a detailed investigation into the adsorption properties of the functional groups on the (001) surface. A further comprehensive investigation was carried out to determine how changes in the nitrogen and oxygen atoms in the crown ether framework influence its adsorption affinity to barium ions. In addition, a detailed analysis was carried out to elucidate the molecular interactions between crown ethers with pyridine carboxylic acid side chains and barium sulfate. The newly developed decalcifying macrocycle descaling agent exhibited superior adsorption performance, achieving an adsorption energy for barium ions approximately −4.1512 ev higher than that of conventional DTPA decalcifiers. This remarkable improvement is mainly attributed to the pivotal role of electrostatic forces in the coordination process between the macrocycle descaling agent and barium ions, with an electrostatic potential value reaching −143.37 kcal/mol. This discovery not only introduces a novel approach to the removal of barium sulfate scale but also highlights the significant potential of macrocycle chemistry in industrial applications. Full article

Ambitious approaches to science teaching feature collaborative learning environments and engage students in rich discourse to make sense of their own and their peers’ ideas. Classroom assessment must cohere with and mutually reinforce these kinds of learning experiences. This paper explores how teachers’ enactment of formative assessment tasks can support such an ambitious vision of learning. We draw on video data collected through a year-long investigation to explore the ways that co-designing formative assessments linked to a learning progression for modeling energy in systems could help teachers coordinate classroom practices across high school physics, chemistry, and biology. Our analyses show that while there was some alignment of routines within content areas, students had differential opportunities to share and work on their ideas. Though the tasks were constructed for surfacing students’ ideas, they were not always facilitated to create space for teachers to take up and work with those ideas. This paper suggests the importance of designing and enacting formative assessment tasks to support ambitious reform efforts, as well as ongoing professional learning to support teachers in using those tasks in ways that will center discourse around students’ developing ideas. Full article