New Journal of Chemistry最新文献

A T-shaped cyanidometal-bridged tetranuclear one-electron oxidized complex [{CpFe^II(dppe)(CN)}₃Ru^III(DMPZ)₂Cl][PF₆]₂ (1⁺, Cp = cyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; DMPZ = 2,6-dimethylpyrazine), which can be considered as a composition of cis- and trans-configuration trinuclear subunits, was synthesized and well characterized. The FTIR and UV-vis-NIR spectra of products of 1⁺ with different valence states were investigated by spectroelectrochemical measurements on an OTLLE cell in dichloromethane. (TD)DFT calculations were performed to fully understand the metal-to-metal charge transfer (MMCT) transition and delocalization properties of the T-shaped cyanidometal-bridged tetranuclear complexes. Spectral analyses revealed a superior electronic delocalization between the terminal Fe centers positioned in the trans-configuration compared to those in the cis-configuration. Most importantly, this work shows the presence of the oxidation-driven intramolecular charge transfer from the terminal Fe center to the central Ru center during the change from the two-electron oxidized state (1²⁺) to the three-electron oxidized state (1³⁺), as confirmed by electrochemistry, FTIR and UV-vis-NIR spectroscopy, and also strongly supported by theoretical calculations.

ZrO₂-(NH₄)₃PW₁₂O₄₀ composites (ZW-X) were successfully prepared after annealing at temperatures ranging from 250 °C to 450 °C for the degradation of organic dyes. A thorough investigation was conducted to evaluate the impact of calcination temperature on the structural configuration, morphological properties, bandgap energetics, and charge transfer behaviors of the ZW composites. The results revealed that ZW-350 achieved an optimal structural configuration through the formation of heteropoly blue (HPB) after calcination at 350 °C for 2 h. Notably, the ZW-350 photocatalyst exhibited exceptional photocatalytic activity towards rhodamine B (RhB) and methylene blue (MB) under both ultraviolet and simulated solar irradiation. Furthermore, RhB could be efficiently photodegraded in various water bodies using ZW-350. These remarkable performances can be attributed to the formation of a type-II heterojunction between ZrO₂ and HPB within the ZW-350 composites. During the photodegradation process of RhB, hydroxyl radicals (˙OH), superoxide radicals (˙O₂⁻), and photo-generated holes (h⁺) were identified as the primary active species. This study presents a novel method for the preparation of advanced HPB-based materials for the degradation of organic pollutants.

The first examples of well-defined, tetrasubstituted bis-guanidinate-supported, air- and moisture-stable, monomeric boron complexes – namely, L^1–3Bpin (1a–1c), L¹BCat (2), 3, 4a, 4b and 5 (where L^1–3 = {(ArHN)(ArN) CN C(NAr)(NHAr)}; DepBG = L¹; Ar = 2,6-Et₂-C₆H₃, MesBG = L²; Ar = 2,4,6-Me₃-C₆H₂, XylBG = L³; Ar = 2,6-Me₂-C₆H₃) – are reported. A reaction between pinacolborane (HBpin) and catecholborane (HBcat) with free bis-guanidine ligands yielded compounds 1a–1c and 2, respectively. Additionally, the reaction of in situ generated 2,2,-biphenoxyborane, naphtho[2,3-d]-1,3,2-dioxaborolane and naphtho[1,8-de]-1,3,2-dioxaborinane with 1.0 equivalent of L¹H or L³H afforded compounds 3, 4a, 4b (with L³H) and 5, respectively. All the newly synthesized compounds (1a–1c, 2, 3, 4a, 4b and 5) were characterized by multinuclear NMR, and HRMS. Additionally, compounds 1a–1c, 2, 3, 4a and 4b were characterized by single-crystal X-ray diffraction studies. The solid-state structures reveal that all these boron complexes are monomeric. Furthermore, photophysical studies were conducted for boron complexes 1a, 2, 3, and 4a, which showed a maximum relative fluorescence quantum yield of 9.2% in THF for 4a. These photophysical properties were further evaluated using theoretical calculations.

The hemihydrate of the Schiff base derived from 4-hydroxybenzaldehyde and 4-aminobenzoic acid was synthesized and characterized using TG, ATR-FTIR, and SCXRD methods. Thermal analysis shows that the dehydration of 4-{(E)-[(4-hydroxyphenyl)methylidene]amino}benzoic acid hemihydrate occurs around 150 °C and yields a non-crystalline anhydrous form (m.p. = 241 °C). ATR-FTIR studies confirm the presence of an azomethine group (–HCN–). SCXRD experiments revealed that the title compound crystallizes in the monoclinic P2₁/n space group with two 4-(4-hydroxybenzylidene)aminobenzoic acid molecules and one water molecule in the asymmetric unit. In the crystal of the title compound, the Schiff base molecules are linked via O–H⋯O, O–H⋯N, and C–H⋯O hydrogen bonds, and C–H⋯π and π–π interactions. ADMET analysis indicates the synthesized compound's potential as a promising agent with high gastrointestinal absorption and the ability to cross the blood–brain barrier. Molecular docking studies predict its binding to the active sites of AChE and CA II.

Purpose: monitoring the solubilities of pharmaceuticals is a critically important bottleneck for their development, since it influences their efficacy and bioavailability. To overcome this challenge, we leverage a machine learning (ML) technique to forecast and optimize solubility in compounds related to ibuprofen. Method: our comprehensive dataset, comprising over 1126 data points acquired from the literature, was analyzed using molecular descriptors extracted from molecular electrostatic potentials (MEPs), Lipinski's rule of five, and hydrogen bonding parameters. EdgeCov, linear, and random forest regression – three of the best ML models, achieved remarkable predictive power, with R² values ranging from 0.86 to 0.92 and root mean square errors (RMSEs) between 0.002 and 0.34. Results: with compounds exceeding 80 g L⁻¹, solubility mapping revealed a significant correlation between hydroxyl groups and enhanced solubility. Our study illustrates the potential for ML-driven design to streamline pharmaceutical development, predicting aqueous solubility prior to manufacturing and conserving valuable resources. By identifying appropriate molecular attributes, our approach enables the rational design of solubility-optimized pharmaceuticals, promoting bioavailability and therapeutic efficacy. Conclusion: this innovative framework accelerates the discovery of effective, solubility-optimized medications with broad implications for pharmaceutical research and development.

Bacterial resistance and osteogenic activity are crucial requirements for titanium (Ti) dental implants during their practical use in clinical applications. In this work, a layer consisting of positively charged chitosan quaternary ammonium salt (QCS), negatively charged polyacrylic acid (PAA) and zinc gluconate was well constructed via a layer-by-layer (LbL) procedure. After surface modification, the layer exhibited a significant reduction of approximately 46° in the water contact angle, demonstrating enhanced hydrophilicity. The modified surface further demonstrated excellent thermal stability at a sterilization temperature of 115 °C. Owing to the consistent release of Zn²⁺, the structurally optimized QCS/PAA-Zn²⁺ coating achieved a remarkable antimicrobial activity of 97% against S. aureus. Moreover, its antibacterial efficacy remained highly effective, with an inhibition rate of 85%, even after cycling tests. The excellent biocompatibility and osteogenic activity of the layer were further proved by a cellular experiment. Our results may provide guidance for the upgradation of Ti-based implant coatings.

Herein, we report the design and synthesis of two new 8-hydroxyquinoline platinum(II) derivatives, namely [Pt(QCl)Cl₂]·CH₃OH (YLN1, YLN = Yulin Normal University) and [Pt(QBr)Cl₂]·CH₃OH (YLN2), with 2-[(5-chloropyridin-2-yl)-hydrazonomethyl]-quinolin-8-ol (QCl) and 2-[(5-bromopyridin-2-yl)-hydrazonomethyl]-quinolin-8-ol (QBr) as ligands, respectively. The cytotoxicity of YLN1 and YLN2 against MDA-MB-231 breast cancer cells (IC₅₀ = 5.49 ± 0.14 μM and 7.09 ± 0.24 μM) was found to be generally higher than against noncancer HL-7702 cells (IC₅₀ > 20.0 μM). Moreover, YLN1 and YLN2 induced senescence and apoptosis in MDA-MB-231 (MM231) cancer cells by significantly triggering DNA damage and downregulating hTERT mRNA expression, and the antitumor mechanisms of the Pt(II) complexes with different QCl and QBr ligands follows the order of YLN1 > YLN2. Taken together, we found the two new 8-hydroxyquinoline platinum(II) derivatives YLN1 and YLN2 as specific anticancer drugs targeting DNA damage response and hTERT suppression.

BN-containing molecules have attracted great attention in the past few decades due to their intriguing electronic and optoelectronic properties. Herein, three novel functionalized donor–acceptor (D–A) type luminophores, i.e., aminoboranes containing phenothiazyl substituents 4a, 4b, and 4c with similar structures, were obtained. These aminoborane derivatives showed good air/moisture stability and lower LUMO energy levels than those of CN-containing compound 4d. The results revealed that these aminoborane derivatives exhibited interesting photophysical behavior including aggregation-induced emission (AIE). More importantly, the addition of fluoride ions to diarylboryl–phenothiazines induced a rapid change in the emission color from blue to yellow accompanied by strong intensity changes. Compared to the BN-containing compounds, the CN-containing compound 4d did not show any evident AIE properties and fluoride ion sensing characteristics.

A straightforward, modular, and high yielding synthetic protocol for accessing bis(N-heterocyclic carbene)s incorporating alkyl and aryl N-substituents with varied steric profiles, as well as flexible dimethylsilane and dimethylsiloxane linkers is presented. This provides a more direct entry to both new and reported chelating bis(carbene) ligands. The incorporation of dimethylsilicon fragments rather than linear alkyl chains in the linker is expected to enhance the chelating properties of the ligand by means of the Thorpe–Ingold effect.

The rise of non-toxic inorganic metal halide perovskites has become significant for commercializing optoelectronic products and solar cells based on perovskite technology. This inquiry explores the structural, mechanical, electronic, and optical characteristics of emerging environmentally friendly Mg₃BX₃ (B = P, N; X = Br, I) perovskites through first-principles density functional theory (DFT). The structural investigation revealed that the dimensions of the lattice and the volumes of the cells expand as the size of the halogen and cation atoms rises. The electronic band structures obtained via the GGA-PBE and HSE06 functionals unveil the indirect band gap upon substituting each of the anions (Br, I) and cations (P, N), and these atoms influence the variation of the energy bandgaps. Besides, halides and cations influence the foundations of bandgap transformation and the modulation of the energy gaps, which are elucidated by analyzing both the partial and total density of states. According to the optical findings, each of the compounds exhibits minimal reflectivity (less than 24% within the visible spectrum and less than 36% at 0 eV), a significant absorption coefficient (highest around 0.58 × 10⁵ cm⁻¹ inside the visible spectrum and 3.01 × 10⁵ cm⁻¹ in the UV spectrum) and elevated conductivity within both the visible and UV spectrum, rendering these compounds appropriate for multi-junction solar cells, optoelectronic devices, and other UV applications. Moreover, the optical investigation presents that Mg₃NI₃ shows remarkable absorption and conductivity insights within the visible spectrum. Furthermore, the assessment of the mechanical durability of each compound is executed using Born stability criteria, phonon dispersion curves, and the formation enthalpy. All entities display mechanical integrity, directional dependence, and brittleness throughout the elastic investigations.