Inorganics

Cisplatin’s chemotherapy is hindered by drug resistance and toxicity, making copper complexes a potential alternative. A novel copper(II) complex, [CuLBr], was synthesized from a tetradentate vicinal dioxime ligand (H₂L) and characterized. [CuLBr] features a distorted square pyramidal geometry with a CuN₄Br chromophore. DFT calculations showed a narrowed HOMO-LUMO gap and increased electrophilicity, enhancing its chemical reactivity. [CuLBr] exhibited potent biomimetic catalytic activity, functioning as an efficient superoxide dismutase mimic and catalase mimic. Biophysical studies (UV-Vis, fluorescence, and viscosity) demonstrated a strong, spontaneous affinity of [CuLBr] for calf thymus DNA and Human Serum Albumin, suggesting groove-binding and static quenching mechanisms. In vitro assays revealed superior anticancer activity against HepG-2, HCT-116, and MDA-MB-231 cell lines, with greater selectivity than the free ligand and doxorubicin. Molecular docking studies reveal a high binding affinity of [CuLBr] with key proteins, including ferredoxin-1 and VEGF. This may suggest potential dual mechanisms of action, involving the induction of cuproptosis and the inhibition of tumor angiogenesis. These findings position [CuLBr] as an effective multi-metal-based anticancer agent with advantageous selectivity.

While many [FeFe]-hydrogenase biomimetics are effective proton-reduction catalysts, few are active for H₂ oxidation, and examples containing both a pendant amine group, able to act as a proton relay, and a second redox center, both essential features of the enzymes, are rare. Here we report the preparation and oxidation chemistry of two ferrocene-functionalized amino-diphosphines (PCNCP), (CH₂PR₂)₂NCH₂Fc (R = Ph (1), Cy (2)), and their ethylenedithiolate (edt) diiron complexes, [Fe₂(CO)₄(μ-edt){κ²-(R₂PCH₂)₂NCH₂Fc}] (R = Ph (3), Cy (4)). Their crystallographic characterization shows that PCNCP occupies an apical–basal position. CV responses are slightly R-dependent, showing for 3 and 4 in three separate oxidative processes assigned to successive one-electron oxidation of the diiron core (quasireversible), appended Fc (reversible), and the amine–diiron moiety (irreversible), as confirmed by IR and UV–Vis spectroelectrochemical studies supported by Density Functional Theory (DFT) and Time-dependent Density Functional Theory (TDDFT) calculations. The first oxidation results in a structural rearrangement of the Fe(PNP)(CO) unit and the formation of a semi-bridging carbonyl. Slow protonation of 3 with HBF₄∙Et₂O affords the corresponding N-protonated cation in acetone, whilst μ-hydride products dominate for both 3 and 4 in CD₂Cl₂. A preliminary H₂ oxidation study was carried out with 3, and while there was some evidence of activity, it was much lower than reported for alkyl-functionalized PCNPC diiron derivatives.

A novel catalyst, Tm₂FeSbO₇, was synthesized by employing the solid-phase high-temperature sintering method, and, for the first time, it was utilized to create a Z-type heterojunction with BiYO₃. A direct Z-scheme Tm₂FeSbO₇/BiYO₃ heterojunction photocatalyst (TBHP) was successfully produced by employing the ball-milling technique. X-ray diffraction analysis results indicated that Tm₂FeSbO₇ crystallized in a cubic pyrochlorestructure which owned the Fd-3m space group, with a unit cell parameter of 10.1769 Å, whereas BiYO₃ displayed a fluorite structure in the Fm-3m space group, with a unit cell parameter of 5.4222 Å. The Mossbauer spectrum of Tm₂FeSbO₇ showed that Fe³⁺ ions might locate at octahedral sites. The measured bandgap widths for the TBHP, Tm₂FeSbO_7, and BiYO₃ were 2.14 eV, 2.21 eV, and 2.30 eV, respectively. Multiple experimental results demonstrated that the TBHP exhibited a higher valence band ionization potential, a narrower band gap width, and a higher removal efficiency of the sulfamethoxazole (SMX) compared with the Dy₂TmSbO₇/BiHoO₃ heterojunction photocatalyst. Under visible-light irradiation (VISLI) of 115 min, the TBHP showcased exceptional photocatalytic elimination performance; therefore, the elimination rate of the SMX and the total organic carbon (TOC) mineralization rate reached 99.51% and 98.10%, respectively. In contrast to single-component Tm₂FeSbO₇, BiYO_3, or conventional nitrogen-doped titanium dioxide (N-TiO₂) catalyst, the TBHP exhibited removal efficiency enhancement for degrading the SMX by 1.17 times, 1.31 times, or 4.06 times. Simultaneously, the matching mineralization rate for removing the TOC density by employing the TBHP was 1.20 times, 1.34 times, or 4.73 times higher than that by employing Tm₂FeSbO₇, BiYO₃, or conventional N-TiO₂. Above experimental results indicated that the mineralization efficiency for removing TOC density by employing the TBHP was higher than that by employing Tm₂FeSbO₇, BiYO₃, or N-TiO₂. Radicals trapping experiments and the electron paramagnetic resonance spectroscopy results revealed that hydroxyl radicals, superoxide anions, and photoinduced holes were the primary active species during the catalytic elimination course of the SMX by employing the TBHP under VISLI. The results demonstrated that the direct Z-scheme TBHP, which was developed in this study, exhibited the maximal removal efficiency for degrading the SMX in contrast to Tm₂FeSbO₇, BiYO₃, or N-TiO₂. Additionally, the possible elimination routes and elimination mechanisms of the SMX were proposed. Therefore, an important scientific foundation for developing high-performance heterojunction catalysts was established.