INVESTIGATIONS ON BIOLOGICAL EFFECT OF POLARIZED LIGHT

Abstract— The biological effects of single and 4-time irradiation of primary human embryo fibroblasts with 4 J/cm² polarized light emitted by a halogen light source were investigated. The functional state of the plasma membrane was examined by means of lectin-binding and polycationized ferritin-binding techniques. It was established that the Con A binding of the cells did not change, whereas the number of negatively charged binding sites increased to a significant degree in relation to the untreated (control) samples and cell cultures exposed to diffuse (non-polarized) light. The micromorphological examinations showed no ultrastructural deviations. The quantitative increase of negative surface charges may be regarded as an indication of the biological effect of polarized light exerted on the cell membrane. The modifying effect of polarized light on the survival of E. coli exposed to the ionizing radiation was manifested in decreased anoxic radiation response.     

Synthesis and characterization of novel Cd(II), Zn(II) and Ni(II) complexes with 2-quinolinecarboxaldehyde selenosemicarbazone. Crystal structure of bis(2-quinolinecarboxaldehyde selenosemicarbazonato)nickel(II)

New complexes of Cd(II), Zn(II) and Ni(II) with 2-quinolinecarboxaldehyde selenosemicarbazone (Hqasesc) were synthesized and structurally characterized. The structure of the ligand, Cd(II) and Zn(II) complexes was determined by NMR and IR spectroscopy, elemental microanalysis and molar conductivity measurements. Both complexes occur in solution in two forms, the major tetrahedral and minor octahedral. In the major Cd(II) complex one qasesc⁻ ligand is coordinated as a tridentate, the fourth coordination site being occupied by acetate, while in the major Zn(II) complex two qasesc⁻ ligands are coordinated as bidentates. In both minor complexes two qasesc⁻ ligands are coordinated as tridentates forming the octahedral geometry around the central metal ion. The only paramagnetic complex in the series is Ni(II) complex for which X-ray structure analysis was performed. The complex has the angularly distorted octahedral geometry with two qasesc⁻ ligands coordinated as tridentates, in a similar way as in the minor complexes of Cd(II) and Zn(II).     

Unusual methylation reaction of gem-bromofluorospiropentanes with methyllithium

A series of novel gem-bromofluorospiropentanes were synthesized and investigated in the reaction with methyllithium. Either substitution of the fluorine atom for a methyl group or rearrangement into methylated cyclobutene derivatives occurred under these conditions.     

Volatile Phthalocyanines: Vapor Pressure and Thermodynamics

The current review summarizes the data of saturated vapor pressure and thermodynamic parameters of the sublimation process of different phthalocyanines as reported in the literature as well as in our work. The volatility of phthalocyanines is analyzed from the standpoint of their molecular and crystal structure. The differences in the saturated vapor pressure value of the investigated phthalocyanines may reach some orders of magnitude and are determined by the Van der Waals and electrostatic interaction of the peripheral atoms of adjacent molecules, as well as to a specific interaction, the type and number of which depend on the type of molecules packing in the crystal.     

Structure-based design and in-parallel synthesis of inhibitors of AmpC beta-lactamase.

BACKGROUND: Group I beta-lactamases are a major cause of antibiotic resistance to beta-lactams such as penicillins and cephalosporins. These enzymes are only modestly affected by classic beta-lactam-based inhibitors, such as clavulanic acid. Conversely, small arylboronic acids inhibit these enzymes at sub-micromolar concentrations. Structural studies suggest these inhibitors bind to a well-defined cleft in the group I beta-lactamase AmpC; this cleft binds the ubiquitous R1 side chain of beta-lactams. Intriguingly, much of this cleft is left unoccupied by the small arylboronic acids. RESULTS: To investigate if larger boronic acids might take advantage of this cleft, structure-guided in-parallel synthesis was used to explore new inhibitors of AmpC. Twenty-eight derivatives of the lead compound, 3-aminophenylboronic acid, led to an inhibitor with 80-fold better binding (2; K(i) 83 nM). Molecular docking suggested orientations for this compound in the R1 cleft. Based on the docking results, 12 derivatives of 2 were synthesized, leading to inhibitors with K(i) values of 60 nM and with improved solubility. Several of these inhibitors reversed the resistance of nosocomial Gram-positive bacteria, though they showed little activity against Gram-negative bacteria. The X-ray crystal structure of compound 2 in complex with AmpC was subsequently determined to 2.1 A resolution. The placement of the proximal two-thirds of the inhibitor in the experimental structure corresponds with the docked structure, but a bond rotation leads to a distinctly different placement of the distal part of the inhibitor. In the experimental structure, the inhibitor interacts with conserved residues in the R1 cleft whose role in recognition has not been previously explored. CONCLUSIONS: Combining structure-based design with in-parallel synthesis allowed for the rapid exploration of inhibitor functionality in the R1 cleft of AmpC. The resulting inhibitors differ considerably from beta-lactams but nevertheless inhibit the enzyme well. The crystal structure of 2 (K(i) 83 nM) in complex with AmpC may guide exploration of a highly conserved, largely unexplored cleft, providing a template for further design against AmpC beta-lactamase.     

A new dimerization reaction producing 2‐amino‐9‐oxopyrrolo‐[2,1‐b]quinazoline‐1‐carbonitriles and analogous pyrrolo‐[1,2‐a]thieno[3,2‐d] pyrimidinecar bonitriles

A series of 2‐alkylthio‐4‐oxo‐3‐quinazolineacetonitriles 4 and 2‐alkylthio‐4‐oxothieno[3,2‐d]pyrimidine‐3‐acetonitriles 8 was prepared. Upon treatment with sodium hydride, compounds 4 and 8 react to give 2‐amino‐4,9‐dihydro‐9‐oxopyrrolo[2,1‐b]quinazoline‐1‐carbonitriles 9 and 6‐amino‐4,9‐dihydro‐9‐oxopyrrolo[1,2‐a]thieno[3,2‐d]pyrimidine‐7‐carbonitriles 10 , respectively. The transformation of compounds 4 and 8 to the tricyclic aminonitriles 9 and 10 involves a dimerization step followed by a pyrrole cyclization. The tert‐butyl ester derivatives 4d and 8d upon treatment with sodium hydride underwent a Thorpe‐Ziegler cyclization to provide enaminoesters of fused 1,3‐thiazines ( 16 and 17 , respectively) as major products.     

Phenomenological modeling and intensification of texturing/grinding-assisted solvent oil extraction: case of date seeds (Phoenix dactylifera L.)

Accelerated Solvent Extraction (ASE) and Dynamic Maceration (DM) were used with n-hexane to study the extraction of oil from date seed powders with different particle sizes. The intensification was studied with instant controlled pressure drop (DIC) as texturing pretreatment. DM yields increased from 4.57% to 10.49 ± 0.05% dry–dry basis (ddb) when particle size decreased from 1.4 to 0.2 mm. For coarsely grounded seed powder, ASE oil yields were 11.35 ± 0.05% ddb and 14.15% ddb for untreated and DIC date-seeds, respectively. Optimized DIC pretreatment allowed the smallest particle size powder to get 15.2 ± 0.05% ddb as ASE yields, while the 2-h DM yields increased from 4.67 to 11.62 ± 0.05% ddb for particle size decreased from 1.4 to 0.2 mm, respectively. Fundamental analysis of various powders was achieved through washing–diffusion phenomenological model. DIC texturing implied higher washing stage, with relative starting accessibility %δY_s of 70% against 55% for untreated particles. Consequently, the diffusion stage time was dramatically reduced, without great modification of effective diffusivity D_eff value. Therefore, DIC ground seeds greatly enhanced the mass transfer mechanism. The evaluation of starting accessibility δY_s enables to establish an empirical relationship between δY_s and particle diameter δY_s = f(D). Finally, DIC texturing did not imply any modification of the lipid profile.