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Importantly, the h+ and •O2- active species play a deterministic role in promoting the degradation of the RhB dye. Compared to commercial ZnO nanoparticles, the developed nanoparticles exhibit superior photocatalytic activities, further elaborating that the Sm3+-activated BiOF nanoparticles are poised to be one of most promising visible light-driven photocatalyst candidates.It is urgent to find a catalyst with high selectivity and efficiency for the reduction of CO2 by renewable electric energy, which is the important means to reduce the greenhouse effect. In this work, we report that the metal-organic framework (MOF) indium-based 1,4-benzenedicarboxylate (In-BDC) catalyzes CO2 to formate with a Faradaic efficiency (FEHCOO-) of more than 80% in a wide voltage range between -0.419 and -0.769 V (vs. reversible hydrogen electrode, RHE). In-BDC performs at a maximum FEHCOO- of 88% at -0.669 V (vs. RHE) and a turnover frequency of up to 4798 h-1 at -1.069 V (vs. RHE). The long-term durability of 21 h and reusability of the electrocatalyst are clearly demonstrated. It opens up a new opportunity to utilize MOF with novel metal motifs for the efficient electroreduction of CO2.Six organic-inorganic hybrid pyridine-4-carboxylate-decorated organotin (OT)-lanthanide (Ln) heterometallic antimotungstates [Ln(H2O)6(pca)]H[Sn(CH3)2(H2O)]3[B-β-SbW9O33]·12H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3), Nd3+ (4), Sm3+ (5), Eu3+ (6); Hpca = isonicotinic acid] have been prepared with the help of the structure-directing effect of the trivacant [B-α-SbW9O33]9- segment toward [(CH3)2Sn]2+ and Ln3+ ions in an acidic water medium. The prominent architecture characteristic is that their structural units consist of a trivacant [B-β-SbW9O33]9- segment stabilized by three [Sn(CH3)2(H2O)]2+ groups and a [Ln(H2O)6(pca)]2+ cation, which are interconnected to propagate an intriguing two-dimensional (2D) network. For all we know, 1-6 stand for the first 2D OT-Ln heterometallic polyoxometalates. Furthermore, luminescence performances of solid-state 3-6 were deeply surveyed at ambient temperature. Energy migration from [B-β-SbW9O33]9- and pca- to Sm3+ centers in 5 was also studied. Comparative studies demonstrate that the contribution of [B-β-SbW9O33]9- sensitizing the emission of Sm3+ is prominently larger than that of pca- sensitizing the emission of Sm3+ in the emission process of 5. Most interestingly, 6 as a fluorescence probe exhibits high selectability and sensitivity for recognizing Zn2+ and Cu2+ in water.Experimentally measured rate constants, k12obsd, for the reductions of [Ni(III)tripeptides(H2O)2] with Fe(CN)64-, Mo(CN)84-, and W(CN)84- are 102 to 105 times faster than the calculated rate constants with the Marcus theory for outer-sphere electron-transfer processes, k12calc, even when work terms are considered. This gives rise to a kinetic advantage of k12obsd/k12calc = 102-105, which is consistent with an inner-sphere electron-transfer mechanism via a bridged intermediate. In addition, k12obsd values are nearly independent of the electrochemical driving force of the reactions. This is consistent with one of the two axial water ligands coordinated to [Ni(III)tripeptides(H2O)2] being substituted in the rate-limiting step to form bridged intermediates of the type [(CN)5or7M-(CN)-NiIII(tripeptide)(H2O)]4- with M = FeII, MoIV, or WIV. A limiting rate constant of H2O replacement from [Ni(III)tripeptides(H2O)2] of (5 ± 2) × 107 M-1 s-1 at 25.0 °C is observed. Electron paramagnetic resonance spectra of Ni(III) peptide complexes in the presence of Fe(CN)63-, Mo(CN)83-, or IrCl63- provide evidence for the cyanide-bridged intermediates. Substitution-limited electron-transfer reactions could serve as an additional criterion for inner-sphere pathways when atom or group transfer does not occur during electron-transfer and when precursor and successor complexes cannot be observed directly.Platinum(IV) complexes containing carboxylate and carbamate ligands at the axial position have been reported previously. A better understanding of the similarity and difference between the two types of ligands will provide us with new insights and more choices to design novel Pt(IV) complexes. In this study, we systematically investigated and compared the properties of Pt(IV) complexes bearing the two types of ligands. Ten pairs of unsymmetric Pt(IV) complexes bearing axial carbamate or carboxylate ligands were synthesized and characterized. The stability of these Pt(IV) complexes in a PBS buffer with or without a reducing agent was investigated, and most of these complexes exhibited good stability. https://www.selleckchem.com/products/VX-770.html Besides, most Pt(IV) prodrugs with carbamate axial ligands were reduced faster than the corresponding ones with carboxylate ligands. Furthermore, the aqueous solubilities and lipophilicities of these Pt(IV) complexes were tested. All the carbamate complexes showed better aqueous solubility and decreased lipophilicity as compared to those of the corresponding carboxylate complexes, due to the increased polarity of carbamate ligands. Biological properties of these complexes were also evaluated. Many carbamate complexes showed cytotoxicity similar to that of the carboxylate complexes, which may derive from the lower cellular accumulation but faster reduction of the former. Our research highlights the differences between the Pt(IV) prodrugs containing carbamate and carboxylate axial ligands and may contribute to the future rational design of Pt-based anticancer prodrugs.A family of three picolinate pyclen-based ligands, previously investigated for the complexation of Y3+ and some lanthanide ions (Gd3+, Eu3+), was studied with 161Tb and 177Lu in view of potential radiotherapeutic applications. The set of six Tb3+ and Lu3+ complexes was synthesized and fully characterized. The coordination properties in the solid state and in solution were thoroughly studied. Potentiometric titrations, supported by density functional theory (DFT) calculations, showed the very high stability constants of the Tb3+ and Lu3+ complexes, associated with remarkable kinetic inertness for up to 30 days in 1 M HCl. A complete radiolabeling study performed with both 161Tb and 177Lu radionuclides, including experiments with regard to the stability with and without scavengers and kinetic inertness using challenging agents, proved that the ligands could reasonably compete with the DOTA analogue. To conclude, the potential of using the same ligand for both radiotherapy and optical imaging was highlighted for the first time.
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