Electrocatalytic reduction of CO 2 recently emerged as a viable solution in view of changing the common belief and considering carbon dioxide as a valuable reactant instead of a waste product. In this view, we herein propose the one-step synthesis of gold nanostructures of different morphologies grown on fluorine-doped tin oxide electrodes by means of pulsed-laser deposition. The resulting cathodes are able to produce syngas mixtures of different compositions at overpotentials as low as 0.31 V in CO 2 -presaturated aqueous media. Insights into the correlation between the structural features/morphology of the cathodes and their catalytic activity are also provided, confirming recent reports on the remarkable sensitivity toward CO production for gold electrodes exposing undercoordinated sites and facets.

The generation of hydrogen from water represents an important task towards a carbon neutral economy. Within this context, the preparation of hybrid electrodes merging the versatility of solid-state porous substrates...

Two different high potential Zn(II) porphyrin designs carrying either 4 or 5 meso pentafluorophenyl moieties as electron acceptor groups and a further electron withdrawing branch inserted in either the β (1) or meso (2) position were tested in photoelectrosynthetic cells for HBr splitting. Photoaction spectra in the presence of HBr showed that red photons up to 700 nm could be harvested and converted and that 2 performed better than 1, thanks to better electronic properties of the excited state, favored by the insertion of the benzothiadiazole electron withdrawing group. Photoanodic performances in the presence of HBr, however, remained low, due to inefficient regeneration of the oxidized sensitizer as a result of an insufficient driving force for Br− oxidation.

Novel heteronuclear Ir III −Cu II coordination compounds ([Ir(η 5 -Cp*)Cl 2 Pcfx-Cu(phen)](NO 3 )•1.75(CH 3 OH)•0.75(H 2 O) (1), [Ir(η 5 -Cp*)Cl 2 Pnfx-Cu(phen)](NO 3 )•1.75(CH 3 OH) 4)) bearing phosphines derived from fluoroquinolones, namely, sparfloxacin (Hsfx), ciprofloxacin (Hcfx), lomefloxacin (Hlfx), and norfloxacin (Hnfx), have been synthesized and studied as possible anticancer chemotherapeutics. All compounds have been characterized by electrospray ionization mass spectrometry (ESI-MS), a number of spectroscopic methods (i.e., IR, fluorescence, and electron paramagnetic resonance (EPR)), cyclic voltammetry, variable-temperature magnetic susceptibility measurements, and X-ray diffractometry. The coordination geometry of Ir III in all complexes adopts a characteristic piano-stool geometry with the η 5 -coordinated and three additional sites occupied by two chloride and phosphine ligands, while Cu II ions in complexes 1 and 2 form a distorted square-pyramidal coordination geometry, and in complex 3, the coordination geometry around Cu II ions is a distorted octahedron. Interestingly, the crystal structure of [Ir(η 5 -Cp*)Cl 2 Plfx-Cu(phen)] features the one-dimensional (1D) metal−organic polymer. Liposomes loaded with redox-active and fluorescent [Ir(η 5 -Cp*)Cl 2 Pcfx-Cu(phen)] (1L) have been prepared to increase water solubility and minimize serious systemic side effects. It has been proven, by confocal microscopy and an inductively coupled plasma mass spectrometry (ICP-MS) analysis, that the liposomal form of compound 1 can be effectively accumulated inside human lung adenocarcinoma and human prostate carcinoma cells with selective localization in nuclei. A cytometric analysis showed dominance of apoptosis over the other cell death types. Furthermore, the investigated nanoformulations induced changes in the cell cycle, leading to S phase arrest in a dose-dependent manner. Importantly, in vitro anticancer action on three-dimensional (3D) multicellular tumor spheroids has been demonstrated.

Straightforward electrochemical procedures yielded indium-modified copper cathodes with high activity towards syngas formation via CO2 electroreduction in aqueous electrolytes.

Two novel phosphine ligands, Ph2PCH2N(CH2CH3)3 (1) and Ph2PCH2N(CH2CH2CH2CH3)2 (2), and six new metal (Cu(I), Ir(III) and Ru(II)) complexes with those ligands: iridium(III) complexes: Ir(η5-Cp*)Cl2(1) (1a), Ir(η5-Cp*)Cl2(2) (2a) (Cp*: Pentamethylcyclopentadienyl); ruthenium(II) complexes: Ru(η6-p-cymene)Cl2(1) (1b), Ru(η6-p-cymene)Cl2(2) (2b) and copper(I) complexes: [Cu(CH3CN)2(1)BF4] (1c), [Cu(CH3CN)2(2)BF4] (2c) were synthesized and characterized using elemental analysis, NMR spectroscopy, and ESI-MS spectrometry. Copper(I) complexes turned out to be highly unstable in the presence of atmospheric oxygen in contrast to ruthenium(II) and iridium(III) complexes. The studied Ru(II) and Ir(III) complexes exhibited promising cytotoxicity towards cancer cells in vitro with IC50 values significantly lower than that of the reference drug—cisplatin. Confocal microscopy analysis showed that Ru(II) and Ir(III) complexes effectively accumulate inside A549 cells with localization in cytoplasm and nuclei. A precise cytometric analysis provided clear evidence for the predominance of apoptosis in induced cell death. Furthermore, the complexes presumably induce the changes in the cell cycle leading to G2/M phase arrest in a dose-dependent manner. Gel electrophoresis experiments revealed that Ru(II) and Ir(III) inorganic compounds showed their unusual low genotoxicity towards plasmid DNA. Additionally, metal complexes were able to generate reactive oxygen species as a result of redox processes, proved by gel electrophoresis and cyclic voltamperometry. In vitro cytotoxicity assays were also carried out within multicellular tumor spheroids and efficient anticancer action on these 3D assemblies was demonstrated. It was proven that the hydrocarbon chain elongation of the phosphine ligand coordinated to the metal ions does not influence the cytotoxic effect of resulting complexes in contrast to metal ions type.

In this work, we designed a tetranuclear self-assembled dye 4 (2Z907-Ag+-(Ru(TMAM))) exploiting a combination of the antenna effect and positively-charged groups designed to repel the oxidized form of cationic cobalt redox mediators, in order to reduce recombination and increase the efficiency of dye sensitized solar cells (DSSCs). Charge transfer and excited dynamics were probed by photoelectrochemical and photophysical measurements. The sensitized cell performance, recorded with a [Co(bpy)3]3+/2+ redox mediator and PEDOT counter electrode, showed an improvement when passing from Z907 to the multinuclear systems. The enhancement of the efficiency compared to Z907 resulted mainly from a superior steric and electrostatic shielding determined by the simultaneous presence of long alkyl chains and quaternary ammonia ion units in the architecture of 4.

The phosphine ligand (Ph2PCH2N(CH3)(CH2)2Ph, PNMPEA) obtained by the reaction of the (hydroxymethyl)diphenylphosphine with naturally occurring alkaloid N‐methylphenethylamine, was used to synthesize the half‐sandwich iridium(III) (Ir(η5‐Cp*)Cl2Ph2PCH2N(CH3)(CH2)2Ph, IrPNMPEA) and ruthenium(II) (Ru(η6‐p‐cymene)Cl2Ph2PCH2N(CH3)(CH2)2Ph, RuPNMPEA) complexes. They were characterized using a vast array of methods, including 1D and 2D NMR, ESI(+)MS spectrometry, elemental analysis, cyclic voltammetry (CV), electron spectroscopy in the UV‐Vis range (absorption, fluorescence) and density functional theory (DFT). The initial antimicrobial activity in vitro toward Gram‐positive and Gram‐negative bacterial strains was examined, indicating that both complexes are selective towards Gram‐positive bacteria, e.g., Staphylococcus aureus, where the IrPNMPEA has been more bactericidal compared to RuPNMPEA. Additionally, the interactions of these compounds with various biomolecules, such as DNA (ctDNA, plasmid DNA, 9‐ethylguanine (9‐EtG), and 9‐methyladenine (9‐MeA)), nicotinamide adenine dinucleotide (NADH), glutathione (GSH), and ascorbic acid (Asc) were described. The results showed that both Ir(III) and Ru(II) complexes accelerate the oxidation process of NADH, GSH and Asc that appeared to occur by an electron transfer mechanism. Interestingly, only IrPNMPEA leads to the formation of various biomolecule adducts, which can explain its higher activity. Furthermore, RuPNMPEA and IrPNMPEA have been interacting with the DNA through weak noncovalent interactions.