Homogeneous Precipitation of Lanthanide Oxalates.

Oxalic acid is an important separation agent in the technology of lanthanides, actinides, and transition metals. Thanks to the low solubility of the oxalate salts, the metal ions can be easily precipitated into crystalline material, which is a convenient precursor for oxide preparation. However, it is difficult to obtain oxalate monocrystals due to the fast precipitation. We have developed a synthetic route for homogeneous precipitation of oxalates based on the thermal decomposition of oxamic acid. This work primarily concerns lanthanide oxalates; however, since no information was found about oxamic acid, a brief characterization was included. The precipitation method was tested on selected elements (Ce, Pr, Gd, Er, and Yb), for which the kinetics was determined at 100 °C. Several scoping tests at 90 °C or using different starting concentrations were performed on Ce and Gd. The reaction products were studied by means of solid-state analysis with focus on the structure and morphology. Well-developed microcrystals were successfully synthesized with the largest size for gadolinium oxalate.

Synthesis and Structural Characterisation of an N-Phosphanyl Ferrocene Carboxamide and its Ruthenium, Rhodium and Palladium Complexes.

[((Diphenylphosphanyl)amino)carbonyl]ferrocene (1) has been synthesized and coordinated to light platinum metals, ruthenium, rhodium and palladium, in diverse coordination modes. Specifically, compound 1 was used to prepare the following phosphane complexes, [(η6 -mes)RuCl2 (1-κP)], [(η5 -C5 Me5 )RhCl2 (1-κP)], trans-[PdCl2 (1-κP)2 ], and [(LNC )PdCl(1-κP)] (mes=mesitylene, LNC =[2-(dimethylamino-κN)methyl]phenyl-κC1 ). They were subsequently converted into cationic O,P-chelate complexes by halide abstraction with AgClO4 and into neutral O,P-chelate complexes by deprotonation with potassium tert-butoxide. All coordination compounds and phosphane chalcogenides 1E (P-bound chalcogen atom E=O, S and Se), which were also synthesised, were structurally characterised using spectroscopic methods (IR, multinuclear NMR and ESI MS) and single-crystal X-ray diffraction analysis. The electrochemical behaviour of the prepared compounds was studied by cyclic voltammetry, and the (LNC )Pd-1 complexes were further studied by Mössbauer spectroscopy.

Synthesis and study of Fe → Pd interactions in unsymmetric Pd(ii) complexes with phosphinoferrocene guanidine ligands.

Readily available phosphinoferrocene guanidines coordinate Pd(ii) as P,N-chelating or κ3P,N,Fe-bound ligands. As the latter, they give rise to the first donor-asymmetric complexes featuring Fe-Pd dative bonds, which were studied using direct (spectroscopic and electrochemical) methods and theoretical (DFT) approaches.

Poly[oligo(ethylene glycol) methacrylate]-b-poly[(vinyl benzyl trimethylammonium chloride)] Based Multifunctional Hybrid Nanostructures Encapsulating Magnetic Nanoparticles and DNA.

We report on the preparation of novel and multifunctional hybrid spherical-shaped nanostructures involving a double-hydrophilic block copolymer, namely the neutral cationic poly[oligo(ethylene glycol) methacrylate]-b-poly[(vinyl benzyl trimethylammonium chloride)] (POEGMA-b-PVBTMAC) diblock copolymer, initially complexed with hydrophilic anionic magnetic nanoparticles (MNPs), and subsequently, with short deoxyribonucleic acid (113 bases DNA). The POEGMA-b-PVBTMAC copolymer, the copolymer/MNPs and the copolymer/MNPs/DNA tricomponent hybrid electrostatic complexes were studied by dynamic/electrophoretic light scattering (DLS/ELS) and cryogenic transmission electron microscopy (cryo-TEM) techniques for the determination of their structure and solution properties. The MNPs were complexed efficiently with the oppositely charged diblock chains, leading to well-defined hybrid organic-inorganic spherical-shaped nanostructures. A significant aggregation tendency of the MNPs is noticed in cryo-TEM measurements after the electrostatic complexation of DNA, implying an accumulation of the DNA macromolecules on the surface of the hybrid tricomponent complexes. Magnetophoretic experiments verified that the MNPs maintain their magnetic properties after the complexation initially with the copolymer, and subsequently, within the block polyelectrolyte/MNPs/DNA nanostructures.