Silver(I) Complexes of Two Flexible Bis-phospholane Ligands: Metallamacrocycles,Polymeric Chains,and Metallacryptands

In a 2:2 reaction with silver(I) chloride or bromide, 1,5-bis(1-phospholano)pentane ( 1a ) afforded frame-like macrocyclic structures, with intra- ( 2 , Cl) or intermolecular ( 3 , Br) halido bridges. In contrast, 1,7-bis(1-phospholano)heptane ( 1b ) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis-phospholane and halido ligands. A unique paddle wheel-type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X-ray crystallography.     

Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

Relationship between the Porous Structure Hierarchy and the Physical and Mechanical Properties of Calcium Phosphate Drug Carriers

Russian Physics Journal - A relationship between the structural-morphological and physical-mechanical properties of macro-porous calcium phosphate (CaP) coatings on the surface of titanium implants...     

The coupled-cluster formalism – a mathematical perspective

ABSTRACT

The Coupled-Cluster (CC) theory is one of the most successful high precision methods used to solve the stationary Schrödinger equation. In this article, we address the mathematical foundation of this theory with focus on the advances made in the past decade. Rather than solely relying on spectral gap assumptions (non-degeneracy of the ground state), we highlight the importance of coercivity assumptions – Gårding type inequalities – for the local uniqueness of the CC solution. Based on local strong monotonicity, different sufficient conditions for a local unique solution are suggested. One of the criteria assumes the relative smallness of the total cluster amplitudes (after possibly removing the single amplitudes) compared to the Gårding constants. In the extended CC theory the Lagrange multipliers are wave function parameters and, by means of the bivariational principle, we here derive a connection between the exact cluster amplitudes and the Lagrange multipliers. This relation might prove useful when determining the quality of a CC solution. Furthermore, the use of an Aubin–Nitsche duality type method in different CC approaches is discussed and contrasted with the bivariational principle.     

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

Electron Energy-Loss Spectroscopy Study of the Change in the Free-Electron Density in Thin Superconducting NbN Films under Ion-Beam Irradiation

The change in the free-electron density in ultrathin (5 nm) superconducting NbN films in the initial state and after irradiation by O⁺ ions to doses of (0.1–0.9) × 10¹⁷ cm^–2 has been studied by electron energy-loss spectroscopy (EELS). The analysis has been performed on cross section samples prepared by the focused ion beam method, using plasmon oscillations with energies up to 50 eV. The radiation-induced replacement of nitrogen atoms with oxygen atoms in niobium nitride is found to change the electrical properties of the material, which leads to a decrease in the free-electron density with an increase in the irradiation dose.     

Complex Study of the Spearhead Superficial Crust from Burial Mound no. 1 near Novosvobodnaya Village

A complex study of a spearhead dated back to IV mill. BC from burial mound no. 1 near Novosvobodnaya village (collection of the State Historical Museum) and, in particular, the material of spearhead superficial crust has been performed. The elemental and phase composition of the metal of spearhead and the superficial crust on its surface have been determined by scanning electron microscopy, jointly with energydispersive X-ray microanalysis and X-ray phase analysis. A comparative analysis of the results of studying the spearhead superficial crust and similar crusts on other artifacts from the mounds near Novosvobodnaya village suggest natural origin of the crust on copper?arsenic artifacts.