New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications

The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H₂O)₄[15‐MC_Cu(II)Glyha‐5](Cl)₃ ( 1 (Gd)), Gd(H₂O)₄[15‐MC_Cu(II)Alaha‐5](Cl)₃ ( 2 (Gd)), Gd(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 3 (Gd)) and Gd(H₂O)₃[15‐MC_Cu(II)Tyrha‐5](Cl)₃ ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H₂O)_3,4[15‐MC_Cu(II)Rha‐5]³⁺ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r₁) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM^?1 s^?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications.     

Infrared and auger spectra of dysprosium silicate films

Dysprosium silicate films, Dy _x Si _y O _z , have been investigated using infrared (IR) and Auger spectroscopy. The films have been formed by oxidizing dysprosium metal films on 5.2-nm-thick silicon dioxide films at a temperature of 600°C. It is shown that the composition of the Dy _x Si _y O _z dysprosium silicate films is close to that of dysprosium pyrosilicate, Dy₂Si₂O₇, and irregular in thickness. On going from the film outer surface to the silicon substrate, the amount of dysprosium decreases and that of silicon bound to oxygen increases. Silicon dioxide, SiO₂, predominates in the layer composition near the silicon substrate. The dielectric leakage current density in the accumulation mode is one order of magnitude lower in the Dy _x Si _y O _z films than in the SiO₂ films of the same equivalent thickness due to the larger physical thickness of the former.     

Chemistry of indole

The nitration of indoles containing donor substituents in the 5- and 7-positions in strongly acidic media involves the protonated form and gives primarily compounds with a nitro group in the 6-position. The structures of the products were proved by PMR, UV, and mass spectrometry.     

Quantum chemical study of formation of Cu<Superscript>II</Superscript>–Y<Superscript>III</Superscript> metallamacrocyclic complexes based on glycinehydroximate ligands

The process of solution-phase formation of the Cu^II–Y^III 15-metallacrown-5 complexes bearing the glycinehydroximate ligands has been for the first time investigated by methods of quantum chemistry. The DFT modeling at the B3LYP/DGDZVP (PCM) level was carried out for mono-, bi-, and tri-nuclear copper(II) complexes and also for heteronuclear Cu^II–Y^III derivatives as the metallamacrocycle precursors. The dependence of relative stability of these complexes on the Cu^II and Y^III coordination surroundings and also on the mutual positions of ligands was found. The structural (variations of interatomic distances and valence angles), electronic (changes in the atomic charges and electron density), and thermodynamical (enthalpies and Gibbs free energies) regularities of 15-metallacrown-5 formation were revealed. The key role of Y^III cation was established for the process of formation of the polynuclear metallamacrocyclic compound (15-metallacrown-5).     

Self-control of chaos in neural circuits with plastic electrical synapses

Two kinds of connections are known to exist in neural circuits: electrical (also called gap junctions) and chemical. Whereas chemical synapses are known to be plastic (i. e., modifiable), but slow, electrical transmission through gap junctions is not modifiable, but is very fast. We suggest the new artificial synapse that combines the best properties of both: the fast reaction of a gap junction and the plasticity of a chemical synapse. Such a plastic electrical synapse can be used in hybrid neural circuits and for the development of neural prosthetics, i.e., implanted devices that can interact with the real nervous system. Based on the computer modelling we show that such a plastic electrical synapse regularizes chaos in the minimal neural circuit consisting of two chaotic bursting neurons.     

Dynamical motifs: building blocks of complex dynamics in sparsely connected random networks

Spatiotemporal network dynamics is an emergent property of many complex systems that remains poorly understood. We suggest a new approach to its study based on the analysis of dynamical motifs-small subnetworks with periodic and chaotic dynamics. We simulate randomly connected neural networks and, with increasing density of connections, observe the transition from quiescence to periodic and chaotic dynamics. This transition is explained by the appearance of dynamical motifs in the structure of these networks. We also observe domination of periodic dynamics in simulations of spatially distributed networks with local connectivity and explain it by the absence of chaotic and the presence of periodic motifs in their structure.