Probing dynamics of nanoparticle chains formation during magnetic hyperthermia using time-dependent high-frequency hysteresis loops

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Secondary phosphine oxides as pre-ligands for nanoparticle stabilization

The synthesis of ruthenium nanoparticles (RuNPs) using secondary phosphine oxides (SPOs) as ligands is reported. These easily accessible ligands allow the formation of small nanoparticles in the size range of 1-2 nm which display a high efficiency for hydrogenation of aromatics with TOFs up to 2700 mol h(-1)

The Big Impact of a Small Detail: Cobalt Nanocrystal Polymorphism as a Result of Precursor Addition Rate during Stock Solution Preparation

The control of nanocrystal structures at will is still a challenge, despite the recent progress of colloidal synthetic procedures. It is common knowledge that even small modifications of the reaction parameters during synthesis can alter the characteristics of the resulting nano-objects. In this work we report an unexpected factor which determines the structure of cobalt nanoparticles. Nanocrystals of distinctly different sizes and shapes have resulted from stock solutions containing exactly the same concentrations of [Co{N(SiMe(3))(2)}(2)(thf)], hexadecylamine, and lauric acid. The reduction reaction itself has been performed under identical conditions. In an effort to explain these differences and to analyze the reaction components and any molecular intermediates, we have discovered that the rate at which the cobalt precursor is added to the ligand solution during the stock solution preparation at room temperature becomes determinant by triggering off a nonanticipated side reaction which consumes part of the lauric acid, the main stabilizing ligand, transforming it to a silyl ester. Thus, an innocent mixing, apparently not related to the main reaction which produces the nanoparticles, becomes the parameter which in fine defines nanocrystal characteristics. This side reaction affects in a similar way the morphology of iron nanoparticles prepared from an analogous iron precursor and the same long chain stabilizing ligands. Side reactions are potentially operational in a great number of systems yielding nanocrystals, despite the fact that they are very rarely mentioned in the literature

The big impact of a small detail: Cobalt nanocrystal polymorphism as a result of precursor addition rate during stock solution preparation

The control of nanocrystal structures at will is still a challenge, despite the recent progress of colloidal synthetic procedures. It is common knowledge that even small modifications of the reaction parameters during synthesis can alter the characteristics of the resulting nano-objects. In this work we report an unexpected factor which determines the structure of cobalt nanoparticles. Nanocrystals of distinctly different sizes and shapes have resulted from stock solutions containing exactly the same concentrations of [CoN(SiMe 3) 2 2(thf)], hexadecylamine, and lauric acid. The reduction reaction itself has been performed under identical conditions. In an effort to explain these differences and to analyze the reaction components and any molecular intermediates, we have discovered that the rate at which the cobalt precursor is added to the ligand solution during the stock solution preparation at room temperature becomes determinant by triggering off a nonanticipated side reaction which consumes part of the lauric acid, the main stabilizing ligand, transforming it to a silyl ester. Thus, an innocent mixing, apparently not related to the main reaction which produces the nanoparticles, becomes the parameter which in fine defines nanocrystal characteristics. This side reaction affects in a similar way the morphology of iron nanoparticles prepared from an analogous iron precursor and the same long chain stabilizing ligands. Side reactions are potentially operational in a great number of systems yielding nanocrystals, despite the fact that they are very rarely mentioned in the literature. © 2012 American Chemical Society

Mechanisms of Dipolar Ortho/Para-H2O Conversion in Ice

In this paper a possible explanation for an unexpected ortho.para-water ratio in the gas clouds of comets is given. The description is based on the quantum-mechanical density matrix formalism and the spin temperature concept. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a four spin system, created by two nearest neighbour water molecules, spin eigenstates and their dynamics under the influence of their mutual dipolar interactions are studied. It is shown that a fast conversion between ortho- and para-states occurs on a msec time scale, caused by the intermolecular homonuclear magnetic dipolar interaction. Moreover the spin eigenstates of water in an ice crystal are determined by magnetic dipolar interactions and are not given by normal ortho- and para-H₂O states of gaseous water. As a result of this the spin temperature of gaseous water evaporated from ice depends strongly on its evaporation history and the ortho.para-ratio of water molecules are only an indirect measure of the temperature of ice crystals from where they descend. This result could explain the unexpected experimentally observed ortho.para-ratios in the clouds of comets

Mechanisms of dipolar ortho/para-H2O conversion in ice

In this paper a possible explanation for an unexpected ortho/para-water ratio in the gas clouds of comets is given. The description is based on the quantum-mechanical density matrix formalism and the spin temperature concept. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a four spin system, created by two nearest neighbour water molecules, spin eigenstates and their dynamics under the influence of their mutual dipolar interactions are studied. It is shown that a fast conversion between ortho- and para-states occurs on a msec time scale, caused by the intermolecular homonuclear magnetic dipolar interaction. Moreover the spin eigenstates of water in an ice crystal are determined by magnetic dipolar interactions and are not given by normal ortho- and para-H2O states of gaseous water. As a result of this the spin temperature of gaseous water evaporated from ice depends strongly on its evaporation history and the ortho/para-ratio of water molecules are only an indirect measure of the temperature of ice crystals from where they descend. This result could explain the unexpected experimentally observed ortho/para-ratios in the clouds of comets

Hydrogen generation from alcohols catalyzed by ruthenium-triphenylphosphine complexes : multiple reaction pathways

We report a comprehensive density functional theory (DFT) study of the mechanism of the methanol dehydrogenation reaction catalyzed by [RuH2(H2)(PPh3)3]. Using the B97-D dispersion-corrected functional, four pathways have been fully characterized, which differ in the way the critical beta-hydrogen transfer step is brought about (e.g., by prior dissociation of one PPh3 ligand). All these pathways are found to be competitive (Delta G double dagger = 27.0-32.1 kcal/mol at 150 degrees C) and strongly interlocked. The reaction can thus follow multiple reaction channels, a feature which is expected to be at the origin of the good kinetics of this system. Our results also point to the active role of PPh3 ligands, which undergo significant conformational changes as the reaction occurs, and provide insights into the role of the base, which acts as a "co-catalyst" by facilitating proton transfers within active species. Activation barriers decrease on going from methanol to ethanol and 2-propanol substrates, in accord with experiment.PostprintPeer reviewe