European Journal of Inorganic Chemistry最新文献

The insights into the molecular mechanisms of the primary nucleation of amyloid-β (Aβ) that bind zinc ions are crucial for prevention of toxic early-stage oligomers that yield to Alzheimer's disease. The structural characterization of the polymorphic early-stage zinc-bound Aβ oligomers at the atomic level are unknown due to the limitations of experimental techniques. Here, a comprehensive computational tools are applied to systematically investigate how zinc ions concentration and binding site specificity affect the conformational landscape of polymorphic early-stage Aβ oligomers. The study reveals distinct molecular mechanisms that are influenced by the zinc ions concentrations, zinc-binding sites, and the structure of the polymorphic Aβ dimers. The polymorphic structures of zinc-bound Aβ dimers are determined at the molecular level. The study reveals that zinc ions enhance the rigidity of the polymorphic Aβ dimers and promote structural changes along the hydrophobic domains. Zinc ions selectively decrease hydrogen bonding and increase water solvation in β-sheet-like dimers. Finally, the population is shifted toward zinc-bound random-coil Aβ dimers over zinc-bound β-sheet-structured dimers. The findings provide a molecular-level description of polymorphic zinc-Aβ dimer interactions under various metal:Aβ ratios and distinct binding sites, offering structural insights that may guide the design of future experimental studies on Aβ aggregation.

Heavy main group element compounds with heteronuclear double bonds are of interest due to their fascinating reactivity. Herein, the synthesis of silaphosphenes L¹Ga(X)PSiL² (X = Cl 2a, Me 2b, L¹ = [N(Dipp)C(Me)]₂CH, Dipp = 2,6-ⁱPr₂C₆H₃; L² = PhC(N^tBu)₂) and L¹Ga(Cl)PSiL⁴ 4 (L⁴ = [N(Dipp)C(Me)]₂) is reported, which are obtained from reactions of gallaphosphaketenes L¹Ga(X)PCO (X = Cl 1a, Me 1b) with silylenes L²SiCl and the N-heterocyclic silylene L⁴Si, respectively. In contrast, gallaphosphene L¹GaPSi(Cl)L³ 3 (L³ = DippNC(CH₃)CHC(CH₂)NDipp) formed in the reaction of 1a with the β-diketiminate-substituted silylene L³Si. Silaphosphenes 2a and 4 and gallaphosphene 3 are promising reagents for reactions with nucleophiles and electrophiles as is exemplarily demonstrated with HCl, MeI, MeOTf, MeLi, BnOH, BnNC, and CO₂, respectively.

Two crown ether-appended tetraazanaphthacene derivatives (15CE and 18CE) are synthesized, and their radical anion species (15CE’ and 18CE’) are further obtained by electrocrystallization. Single-crystal X-ray analysis reveals the crystal structures of all metal complexes based on 15CE and 18CE derivatives, which can be modulated by the selection of metal ion salts. 15CE and 18CE can capture metal ions depending on the size of the crown ether moieties to form metal complexes in the crystal state. On the other hand, 15CE’ and 18CE’ are generated by electrocrystallization of 15CE and 18CE using metal salts as the electrolyte, whose imino-N atoms can coordinate to metal ions. As a result, 15CE’ and 18CE’ can work as bridging radical anion ligands to self-assemble into a 3D coordination polymer and a 1D coordination polymer with helical structures, respectively. In particular, the use of both crown ether and the tetraazanaphthacene framework as a bridging radical anion ligand is the essential strategy to expand the diversity of crystal engineering because of being capable of the dramatic change in crystal structures.

Platinum-binding peptides (PtBPs) identified via phage display have emerged as powerful molecular tools for the controlled synthesis and functionalization of nanostructured platinum surfaces. However, the molecular determinants governing their surface recognition, binding strength, and structural adaptability remain incompletely understood. Here, a comparative analysis of five PtBPs, three previously reported (TLTTLTN, SSFPQPN, TLHVSSY) and two newly identified by phage display (TGELSQK, LLVTSVT), using quartz crystal microbalance with dissipation monitoring (QCM-D) and synchrotron radiation circular dichroism (SRCD) spectroscopy, is presented. Adsorption kinetics and binding affinities determined by QCM-D reveal sequence-specific differences in association and dissociation rates, which correlate with the viscoelastic properties of the adsorbed layers. SRCD spectra show that all peptides adopt predominantly disordered conformations in solution but exhibit facet-dependent spectral shifts upon adsorption onto platinum nanoparticles, consistent with conformational adaptation at the interface. The combined data highlight the importance of amino acid composition, kinetic binding parameters, and conformational flexibility in governing Pt–PtBP interactions. This integrated approach provides a deeper understanding of peptide–surface recognition and may support the rational design of sequence-defined biomolecules for use in catalysis, surface modification, and biomedical nanotechnology.

Sulfides constitute an important group of ionic conductive solids for all-solid-state lithium-ion batteries, whereas their poor stability against air and humidity inhibits the accurate experimental evaluation of their intrinsic conductivity. In this paper, a new structural tool, the cluster-plus-glue-atom model, is used to correlate the lithium conduction and crystal structure in sulfide solid-state electrolytes (SSEs). This model identifies the anion-based composition unit in any sulfide as being composed of an anion unit and stoichiometrically matched cations. The anion unit covers a nearest-neighbor anion cluster plus next-neighbor “glue” anions, generally containing 16 or 24 anions. Cations occupy interstitials within the anion unit, with transmission-active Li ions inside anionic triangular dipyramids and octahedra. It is assumed that the Li transmission is realized through adjacent active Li sites of inter-distances falling close to the anion nearest-neighbor distances. The number of such Li–Li pairs per anion (n) is proposed to correlate with room-temperature ionic conductivities (σ) of typical sulfide SSEs. It is revealed for SSEs with 3D Li diffusion channels that the upper limits of the measured σ‘s follow approximately log(σ) = −3 + n/3, enabling a fast evaluation of these SSEs. Accordingly, Li₇SiPS₈, Li₁₀SnP₂S₁₂, and Li₁₀GeP₂S₁₂, with their n's falling in 3–5, should be promising SSEs.

The Front Cover depicts the solvent-dependent hydrogen production pathways during formic acid dehydrogenation, mediated by a ruthenium(II) iminopyridine-ligated complex. The background shows a map of the Braamfontein East Campus of Wits University, with formic acid represented by the Humphrey Raikes building, which houses the School of Chemistry. The two routes lead to hydrogen production, depicted by the iconic Great Hall. More information can be found in the Research Article by A. J. Swarts and co-workers (DOI: 10.1002/ejic.202500212).

A new barium zincophosphite BaZn₂(HPO₃)₃ is obtained via a simple hydrothermal reaction. BaZn₂(HPO₃)₃ crystallizes in the P$$ space group and exhibits a novel 3D crystal structure. It possesses a short ultraviolet cutoff edge of 205 nm, corresponding to a large experimental bandgap of 5.55 eV. BaZn₂(HPO₃)₃ also has good thermal stability. This present work provides a comprehensive characterization of its crystal structure and optical properties. Additionally, first-principles calculations are employed to analyze the structure–activity relationship of BaZn₂(HPO₃)₃.

The Front Cover shows the result of CAS calculations performed on the discrete neutral molecule [Er(sq)(Hsq)(H₂O)₆]. The energy gap between the ground and first excited Kramers doublets was evaluated based on two types of structural modifications to the ErO₈ square antiprism: (1) Isotropic expansion and contraction, where contraction leads to a larger gap, as expected from the stronger crystal field. (2) Anisotropic compression and elongation along the principal axis, both of which result in a wider energy gap. More information can be found in the Research Article by T. Ishida and co-workers (DOI: 10.1002/ejic.202500184).

Ammonia was first discovered as a chemical solvent in the 19th century. Extensive investigations during the 20th century toward its physical and chemical properties have yielded substantial knowledge regarding the compound. Historically, its merit was mainly seen in chemical synthesis and its ability to accommodate syntheses that could not be pursued in aqueous solvents. With a growing demand for low-emission energy systems, the scientific focus on ammonia shifted toward its potential for efficient hydrogen storage and transportation, as well as for direct combustion. Herein, a brief overview of the development of the role of ammonia, with the goal of highlighting its unique properties as a solvent, is provided, in particular, in the chemical syntheses of unprecedented species and reactive compounds.

Nonlinear optical (NLO) crystals play a pivotal role in solid-state lasers and have broad applications in both civilian and military technologies. Ideal NLO crystal materials should possess a wide transmission range, moderate birefringence, a high second-harmonic generation (SHG) coefficient, and excellent physical and chemical stability. Recent research has highlighted that incorporating metals with stereochemically active lone pairs (SCALPs) can significantly improve the NLO performance of these materials. This review presents a comprehensive overview of the latest 20 years’ advancements in NLO crystals featuring SCALPs, with a focus on their crystal structures and optical properties, particularly their SHG responses. The article also explores how metal-based functional units containing SCALPs influence the polarizability of these materials. It is anticipated that this review will provide valuable insights into the functional design of high-performance NLO crystals, contributing to the discovery of new SHG materials with the desired properties to meet the growing demands of modern technologies.