A new phase in the Ag−O−S system

The investigations of reaction between Ag₂SO₄ and Ag₂S in air atmosphere have been carried. Results of DTA and X-ray phase powder diffraction of a reaction mixture have confirmed that in the Ag?O?S system exists a new phase. A formula of the phase is Ag₂SO₂.     

Linear dichroism study of retinoids

Linear dichroism spectra of several retinoids and related polyenes incorporated in stretched polyethylene films were determined. It is suggested that the retinoids are oriented with the plane of the ring parallel to the stretching direction of the film, the long polyene chain being displaced from that direction.     

Measuring acetic acid dimer modes by ultrafast time-domain Raman spectroscopy

Acetic acid is capable of forming strong multiple hydrogen bonds and therefore different dimeric H-bonded structures in neat liquid phase and in solutions. The low frequency Raman spectra of acetic acid (neat, in aqueous solution and as a function of temperature) were obtained by ultrafast time and polarization resolved optical Kerr effect (OKE) measurements. Isotropic OKE measurements clearly reveal a specific totally symmetric mode related to the dimeric structure H-bond stretching mode. The effects of isotope substitution, water dilution and temperature on this mode were investigated. These results together with anisotropic OKE measurements and density functional theory calculations for a number of possible dimers provide strong evidence for the cyclic dimer structure being the main structure in liquid phase persisting down to acetic acid concentrations of 10 M. Some information about the dimer structure and concentration dependence was inferred.     

Synthesis and human leukocyte elastase inhibitory activity of novel 2-spiro(2′,2′-diphenylcyclopropane) cephalosporin sulfones

A new series of 2-spiro(2,2-diphenylcyclopropane) cephalosporin sulfones was synthesizes as potent human leukocyte elastase inhibitors.SynPhar Laboratories Inc., #2 Taiho Alberta Centre, 4290-91A Street, Edmonton, Canada T6R 5V2. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1517–1523, November, 1998.     

Ring-expanded bicyclic β-lactams: a structure-chiroptical properties relationship investigation by experiment and calculations

In the present work, the validity of the helicity rule relating the absolute configuration of the bridgehead carbon atom in bicyclic β-lactams to the sign of the 220 nm band observed in their electronic circular dichroism (ECD) spectra is examined for ring-expanded cephalosporin analogues. To this end, a series of model compounds with a seven-membered ring condensed with the β-lactam unit was synthesized. A key step of their synthesis was either the ring-closing metathesis (RCM) or the free radical cyclization leading to the seven-membered ring with an S, O, or C atom at the 6 position in the bicyclic skeleton. To investigate the scope and limitations of the simple, empirically established helicity rule, a combination of ECD spectroscopy, variable-temperature ECD measurements, X-ray analysis, and time-dependent density functional theory (TD-DFT) calculations was used. A comparison of the experimental ECD spectra with the spectra simulated by TD-DFT calculations gives a reasonable interpretation of the Cotton effects observed in the 240-215 nm spectral range. The results suggest that the helicity rule does not apply to the investigated compounds because of the planarity of their amide chromophore. Thus, these compounds do not constitute an exception to the rule that was established for bi- and polycyclic β-lactams with the nonplanar amide chromophore only.     

ForceFit: A code to fit classical force fields to quantum mechanical potential energy surfaces

The ForceFit program package has been developed for fitting classical force field parameters based upon a force matching algorithm to quantum mechanical gradients of configurations that span the potential energy surface of the system. The program, which runs under UNIX and is written in C++, is an easy‐to‐use, nonproprietary platform that enables gradient fitting of a wide variety of functional force field forms to quantum mechanical information obtained from an array of common electronic structure codes. All aspects of the fitting process are run from a graphical user interface, from the parsing of quantum mechanical data, assembling of a potential energy surface database, setting the force field, and variables to be optimized, choosing a molecular mechanics code for comparison to the reference data, and finally, the initiation of a least squares minimization algorithm. Furthermore, the code is based on a modular templated code design that enables the facile addition of new functionality to the program. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

The design, synthesis, and application of a chiral coupling reagent derived from strychnine for the enantioselective activation of a carboxylic group

The concept of a chiral coupling reagent for the enantioselective synthesis of peptides with a predictable configuration and enantiomeric purity from racemic substrates is presented. The reagent was prepared by treatment of strychninium tetrafluoroborate with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence of sodium bicarbonate yielding N-(4,6-dimethoxy-1,3,5-triazin-2-yl)strychninium tetrafluoroborate in high yield, which is stable at room temperature, and in a broad range of solvents gave enriched Z-Ala-Phe-OMe (dr from 95/5 to 60/40) in high yield with d-configuration on the alanine residue starting from rac-Z-Ala-OH.     

Interaction of methoxy- and methylenedioxyamphetamines with carbon and polymeric adsorbents in polar liquids

Solid phase extraction (SPE) of methoxy- and methylenedioxyamphetamines from diluted aqueous solutions was investigated on carbon and polymeric adsorbents of different textures and chemical compositions. Those adsorbents were applied cartridges packed with three chemically modified carbons prepared from plum stones (initial A2PS, oxidized A2PS-O, and reduced A2PS-H) and commercially available adsorbents (polymeric LiChrolut EN, graphitized Hypercarb and Carboprep). Several factors influence the recovery rates of amphetamine derivatives such as the polarity of adsorbates (free energy of salvation), the specific surface area and surface composition of adsorbents, and the solvent characteristics. Different combinations of these factors affect the recovery rate (R1) for high- and low-surface area adsorbents. The minimal R1 values are observed for an amphetamine derivative at a maximal solvation effect and for a set of amphetamines adsorbed on graphitized carbons.      

New ceramic-carbon composites for electrodes for electrochemical capacitors

A new class of composite materials is introduced. Fine powders of silica, titania, Y-modified zirconia, and three types of alumina were pressed and sintered to form porous monoliths with relatively uniform pore structure. Carbon was then deposited in the pores of such monoliths by thermal decomposition of dichloromethane, cyclohexene, and glucose. The structure of the carbon deposit was studied by low-temperature nitrogen adsorption and by thermal analysis. The composite materials were used as electrodes in electrochemical capacitors with 1-ethyl-3-methylimidazolium trifluoromethylsulfonate (a low-temperature ionic liquid) as the electrolyte. High capacitances were observed for glucose-derived materials, which had high specific surface areas.