Nuclear resonance vibrational spectra of five-coordinate imidazole-ligated iron(II) porphyrinates

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).     

Synthesis and characterization of two homologous series of diastereomeric 2-alkoxyphenylcarbamates

Two homologous series of racemic diastereomeric cis- and trans-(2-dimethylaminomethylcycloheptyl)-2-alkoxyphenylcarbamates with alkyl chain lengths ranging from C? to C? were synthesized by stereoselective reactions. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR and IR spectroscopy and their physico-chemical properties were characterized. The two new series of diastereomeric compounds were tested for their local anesthetic activity and parabolic relationship between the local anesthetic activity and lipophilicity was found for both cis- and trans-series. Interestingly, cis-stereoisomers exhibited higher local anesthetic activity.     

The synthesis of 3,6-diamino-2,3,4,6-tetradeoxy-dl-threo-hexopyranose derivatives,substrates for the synthesis of negamycin

Three synthetic routes to derivatives of 3,6 - diamino - 2,3,4,6 - tetradeoxy - DL - threo - hexopyranose were investigated. Addition of sodium azide in acetic acid to 6 - phthalimido - 5,6 - dihydro - 2 - pyrone gave 4-azido compound (7) of the erythro configuration. From methyl 2,4 - dideoxy - β -dl- erythro - hexopyranoside threo 4 - phthalimido - 6 - phthalimidomethyl - tetrahydro - 2 - pyrone (17) was obtained in three steps in low overall yield. Addition of sodium azide in acetic acid to butyl 6 - oxo - 2 - hydroxy - hex - 4 - enoate followed by methylation, amonolysis of the ester group, and reduction gave methyl 3,6 - diacetamido - 2,3,4,6 - tetradeoxy - α - DL - threo - hexopyranoside (26).     

Formation of the radical-cation of monomer in the photoinduced polymerization of isobutylene in the presence of SnCl4

Spectra of isobutylene with SnCl₄ were studied at the temperature of 113°K in the dark and under illumination. Radical-cations of isobutylene are formed by irradiation of the isobutylene–SnCl₄ mixture in n-heptane substantially more slowly than in the isobutylene–TiCl₄ mixture. Polymerization of isobutylene occurs after increasing the temperature up to the melting point of this mixture. The yield of polymer depends on the duration of preirradiation, while the molecular weight of polyisobutylene (M _η) does not depend on the preirradiation of reaction mixture.     

Hydrodynamics of interaction of particles (including cells) with surfaces

The study of the phenomena related to the motion of particles flowing in the proximity of the wall is pursued for purely cognitive reason as well as for some important practical purposes in various fields of technology, biology and medicine.When small spherical rigid particles move in the direction parallel to the surface their velocity is smaller than that of the fluid and depends on the ratio of the distance from the wall to the particle radius. The velocity of a particle falling down in a vertical cylinder is maximal in an eccentric position. A sphere in contact with the wall remains stationary. Translational velocity of spherical rigid particles the dimension of which are comparable to that of the tube is only slightly dependent of their lateral position. The differences in the flow parameters of deformable particles in comparison with rigid ones depend on the particle and fluid viscosity coefficient. When the particles move perpendicularly toward the wall, their velocity decreases as the particle approaches the surface. The change of particle velocity is inversely proportional to the gap.There are several theories explaining the influence of the channel diameter on the suspension viscosity (sigma phenomenon); a modern approach is based on the analysis of rheological properties of suspensions. The explanations of the Fahraeus effect (i.e. the fact that the concentration of particles flowing in a tube linking two containers are smaller than that in the containers) are based on non-uniform particle distribution in a transverse cross section and on the differences of velocities of particles and medium. The deviation of the velocity profile of a suspension of rigid particles flowing through a tube from the parabolic shape (blunting) does not depend on the flow velocity; as concerns deformable particles, however, this effect is the smaller the greater is the flow velocity.When the Reynolds number for particles is greater than 10^-3, there appears a component of particle velocity perpendicular to the streamline direction.This phenomenon is the cause of the lateral migration of particles. Neutrally buoyant rigid particles migrate to a certain concentrical region situated between the tube axis and the wall (tubular pinch region). Deformable neutrally buoyant particles migrate towards the tube axis, and deformable non-neutrally buoyant particles may move either toward the tube axis or toward the wall.In the research on the influence of the flow delimiting surface on the motion of particles in suspension a considerable progress has recently been made.However, the phenomena in this field are extremely complex. At present, two main types of approach may be distinguished. On a microscopic level direct interactions between particles and surfaces are analyzed. A macroscopic approach consists in treating particle suspension as fluid, and overall influence of the surface on its properties are studied. A comprehensive theory linking these two levels has not yet emerged.     

Flow-injection single-point titration of acids with biamperometric detection at polarized platinum electrodes

Flow-injection single-point titration of acids is based on biamperometric measurement of iodine formed quantitatively in the reaction of iodide with iodate. Results are presented for determination of sulphuric, hydrofluoric, monochloroacetic, formic and acetic acids. The slopes of the calibration plots, which are linear for about 1–10 rum acid, depend on the strength of the acid, decreasing from sulphuric acid to acetic acid. With microcomputer on-line data processing, relative standard deviations were about 0.2%.     

Reversible Clustering of Gold Nanoparticles under Confinement

A limiting factor of solvent‐induced nanoparticle self‐assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions.     

Optical Response of Porous Titania‐Silica Waveguides to Surface Charging in Electrolyte Filled Pores

In this work, we present a novel method for in situ investigation of surface charging and ion transport inside nanopores of titania‐silica waveguide by means of the optical‐waveguide‐lightmode spectroscopy. Porous oxide waveguides show a strong optical response when exposed to electrolyte solutions, and this response is consistent with oxide surface charging due to changes in ionic strength and pH of the solution in contact with the waveguide. The optical response to pH or electrolyte concentration change is stabilized within several minutes when the solution ionic strength is sufficiently high (0.1M ), while it takes two orders of magnitude longer to reach stable optical response at very low ionic strengths (<0.1mM ). The relaxation times at the high ionic strength are still by several orders of magnitude slower than expected from bulk diffusion coefficients of electrolytes in water. Our results indicate that diffusion of electrolytes is severely hindered (and more so with decreasing ionic strength) in charged pores inside waveguides.     

Catalytic Hydrogen Transfer over Magnesia, xv. Preliminary Studies of Active Centers of Catalysts

Reduction of 7-tridecanone and 1-phenyl-1-hexanone by 2-propanol at 573-673 K in the presence of MgO has been studied. Acidic as well as strong and weak basic sites of MgO surface have been blocked in the reaction of the oxide with triethylamine, phenol or benzoic acid (1000 mol/g of catalyst), respectively. Retention of activity of MgO treated with triethylamine or phenol in ketones reduction by 2-propanol has been observed. Only residual activity of MgO poisoned by benzoic acid has been noted. The exclusive participation of moderate basic centers of MgO in catalytic reduction of ketones by 2-propanol has been ascertained.