[Psychoemotional and autonomic states in patients with cholelithiasis]. / Psikhoémotsional'noe sostoianie i vegetativnyi status bol'nykh pri zhelchnokamennoi bolezni.

AIM: To investigate the psychoemotional and autonomic states of patients with biliary system diseases and to determine their significance in the development of cholelithiasis. SUBJECTS AND METHODS: A total of 396 patients with stage 1 cholelithiasis were examined. The results of hepatobiliary ultrasonography, multifractional duodenal probing, followed by macroscopic, microscopic, and biochemical examinations of bile (the total concentration of bile acids and cholesterol, by subsequently calculating the cholate-cholesterol ratio) were used to verify the diagnosis. The functional state of the hepatobiliary system was evaluated by dynamic echocholecystography and dynamic hepatobiliscintigraphy. To characterize the emotional state, the investigators applied indicators of the motivational sphere and orientation of an individual and his/her mental state, such as reactive anxiety, personal anxiety, the levels of depression and neuroticism, and intra-, extraversion. The autonomic state was determined from autonomic tone, autonomic reactivity, and autonomic support. RESULTS: Biliary lithogenesis was found to be related to psychoemotional and autonomic states. In cholelithiasis, there was an increase in reactive and personal anxiety and a predominance of diminished parasympathetic and perverted sympathetic autonomic reactivity. The signs of emotional instability and autonomic dystonia were shown to increase with age and the degree of an autonomic response depended on the severity of mental and emotional disorders. CONCLUSION: The results of these comprehensive studies can reveal new pathophysiological patterns of lithogenic bile formation and enhance our understanding of the pathogenesis of cholelithiasis.

Nanoclusters and nanolines: the effect of molybdenum oxide substrate stoichiometry on iron self-assembly.

The growth of Fe nanostructures on the stoichiometric MoO2/Mo(110) and oxygen-rich MoO2+x /Mo(110) surfaces has been studied using low-temperature scanning tunnelling microscopy (STM) and density functional theory calculations. STM results indicate that at low coverage Fe nucleates on the MoO2/Mo(110) surface, forming small, well-ordered nanoclusters of uniform size, each consisting of five Fe atoms. These five-atom clusters can agglomerate into larger nanostructures reflecting the substrate geometry, but they retain their individual character within the structure. Linear Fe nanocluster arrays are formed on the MoO2/Mo(110) surface at room temperature when the surface coverage is greater than 0.6 monolayers. These nanocluster arrays follow the direction of the oxide rows of the strained MoO2/Mo(110) surface. Slightly altering the preparation procedure of MoO2/Mo(110) leads to the presence of oxygen adatoms on this surface. Fe deposition onto the oxygen-rich MoO2+x /Mo(110) surface results in elongated nanostructures that reach up to 24 nm in length. These nanolines have a zigzag shape and are likely composed of partially oxidised Fe formed upon reaction with the oxygen-rich surface.

Control of the axial coordination of a surface-confined manganese (III) porphyrin complex.

The organization and thermal lability of chloro(5,10,15,20-tetraphenyl porphyrinato)manganese(III) (Cl-MnTPP) molecules on the Ag(111) surface have been investigated under ultra-high vacuum conditions, using scanning tunnelling microscopy, low energy electron diffraction and x-ray photoelectron spectroscopy. The findings reveal the epitaxial nature of the molecule-substrate interface, and moreover, offer a valuable insight into the latent coordination properties of surface-confined metalloporphyrins. The Cl-MnTPP molecules are found to self-assemble on the Ag(111) surface at room temperature, forming an ordered molecular overlayer described by a square unit cell. In accordance with the threefold symmetry of the Ag(111) surface, three rotationally equivalent domains of the molecular overlayer are observed. The primitive lattice vectors of the Cl-MnTPP overlayer show an azimuthal rotation of ±15° relative to those of the Ag(111) surface, while the principal molecular axes of the individual molecules are found to be aligned with the substrate (0(-)11) and ((-)211) crystallographic directions. The axial chloride (Cl) ligand is found to be orientated away from the Ag(111) surface, whereby the average plane of the porphyrin macrocycle lies parallel to that of the substrate. When adsorbed on the Ag(111) surface, the Cl-MnTPP molecules display a latent thermal lability resulting in the dissociation of the axial Cl ligand at ~423 K. The thermally induced dissociation of the Cl ligand leaves the porphyrin complex otherwise intact, giving rise to the coordinatively unsaturated Mn(III) derivative. Consistent with the surface conformation of the Cl-MnTPP precursor, the resulting (5,10,15,20-tetraphenyl porphyrinato)manganese(III) (MnTPP) molecules display the same lattice structure and registry with the Ag(111) surface.

Growth and ordering of Ni(II) diphenylporphyrin monolayers on Ag(111) and Ag/Si(111) studied by STM and LEED.

The room temperature self-assembly and ordering of (5,15-diphenylporphyrinato)nickel(II) (NiDPP) on the Ag(111) and Ag/Si(111)-(√3 × âˆš3)R30° surfaces have been investigated using scanning tunnelling microscopy and low-energy electron diffraction. The self-assembled structures and lattice parameters of the NiDPP monolayer are shown to be extremely dependent on the reactivity of the substrate, and probable molecular binding sites are proposed. The NiDPP overlayer on Ag(111) grows from the substrate step edges, which results in a single-domain structure. This close-packed structure has an oblique unit cell and consists of molecular rows. The molecules in adjacent rows are rotated by approximately 17° with respect to each other. In turn, the NiDPP molecules form three equivalent domains on the Ag/Si(111)-(√3 × âˆš3)R30° surface, which follow the three-fold symmetry of the substrate. The molecules adopt one of three equivalent orientations on the surface, acting as nucleation sites for these domains, due to the stronger molecule-substrate interaction compared to the case of the Ag(111). The results are explained in terms of the substrate reactivity and the lattice mismatch between the substrate and the molecular overlayer.

Ni(II) porphine nanolines grown on a Ag(111) surface at room temperature.

The room temperature growth and ordering of (porphyrinato)nickel (II) (or nickel (II) porphine, NiP) molecules on a Ag(111) surface have been investigated using scanning tunnelling microscopy and low-energy electron diffraction (LEED). At a coverage of one monolayer, NiP molecules form a well-ordered molecular layer, having a hexagonal structure, on the Ag(111) surface. Porphyrin molecules have a flat orientation in this overlayer with the molecular plane lying parallel to the substrate. LEED data obtained from one monolayer of the NiP on the Ag(111) surface show the formation of two mirror domains each rotated either clockwise or anticlockwise by 6 degrees with respect to the substrate. NiP molecules forming a second layer self-assemble into well-ordered and uniformly separated nanolines at room temperature. These nanolines consist of hexagonally ordered NiP molecules and are found to be 1-4 molecules wide, depending on the molecular coverage. The completed second monolayer preserves the same planarity and hexagonal ordering as the first molecular layer but with a 4% lateral relaxation which produces a periodic modulation of approximately 5 nm.

An x-ray absorption and photoemission study of the electronic structure of Ni porphyrins and Ni N-confused porphyrin.

Investigations of chemical bonding and electronic structure features for polycrystalline (porphyrinato)nickel (II) (NiP, the simplest Ni porphyrin), (5,10,15,20-tetraphenylporphyrinato)nickel (II) (NiTPP) and (2-aza-21-carba-5,10,15,20-tetraphenylporphyrinato)nickel (II) (N-confused NiTPP, NiNCTPP) have been performed by means of high-resolution soft x-ray absorption and x-ray photoemission spectroscopy. The Ni 2p(3/2) x-ray absorption spectra show strong π-back-bonding in these compounds leading to a high-energy shift (1.2 eV for the NiP and NiTPP) of the entire absorption structure compared to Ni metal. It has been found that the main absorption line of the Ni 2p(3/2) spectrum of the NiNCTPP is shifted by an additional 0.5 eV to higher energies in comparison with those for other nickel porphyrins. This shift is evidence of stronger back-donation (metal-to-ligand charge transfer) and a smaller effective number of 3d electrons on the central Ni atom in the NiNCTPP as compared to other Ni porphyrins. The confused N atom in the NiNCTPP is of pyrrolic type (protonated nitrogen), which was confirmed by the N 1s absorption and core-level photoemission spectra.