Thermodynamics of silver—silver halide electrodes and thermodynamic solubility products of silver halides in glycerol + water mixtures at different temperatures

The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X⁻, and the standard thermodynamic quantities for the transfer of 1 g-ion of X⁻ from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag⁺ and Ag/AgX, X⁻ electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures.     

A Facile, Expeditious Route to the Benzooxabicyclo[3.2.1]octane System. Application to a Short, High-Yield Synthesis of Filiformin

A facile and efficacious route to the benzooxabicyclo[3.2.1]octane system has been developed and applied to a synthesis of filiformin (1). The cycloaddition of ethylene to the methoxychromone 13 furnished the oxetanol 14 through a tandem cycloaddition and gamma-hydrogen abstraction sequence. Lithium aluminum hydride reduction to the diol 15 followed by acid-catalyzed rearrangement produced benzooxabicyclooctanone (16), arising from exclusive external bond migration. Similarly, ethoxychromone (17) under the same sequence of reactions afforded the homologous bridged ketone 20. For the synthesis of filiformin (1), methoxychromone 24 on ethylene cycloaddition followed by reduction of resultant oxetanol 25 with lithium aluminum hydride furnished diol 10. Acid-catalyzed rearrangement of 10 provided the bridged ketone 11 which was brominated to give 26. This bromo ketone had previously been converted to filiformin (1), and also aplysin 9, and hence, the present work represents a short, high-yield formal synthesis of these sequiterpenes from a single starting material.     

Standard<Emphasis Type="Italic">SU</Emphasis>(5) supergravity grand unification model and predictions

A review is given of the StandardSU(5) supergravity model. This model has passed an important check regarding unification of the electro-weak and the strong couplings using high precision LEP data. It is shown that for a significant domain of the parameter space the model also satisfies constraints on the SUSY spectrum from CDF and LEP, as well as proton stability and cosmological relic density constraints.     

Ion solvation by channel carbonyls characterized by 17O solid-state NMR at 21 T

Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts.     

Synthesis of N-substituted piperazinyl carbamoyl and acetyl derivatives of tetrahydropapaverine: potent antispasmodic agents

The synthesis and structure-activity-relationship (SAR) for a series of N-substituted piperazinyl carbamoyl 7-15 and piperazinyl acetyl 18-26 derivatives of tetrahydropapaverine have been carried out. The general synthetic methods of carbamoyl tetrahydropapaverine analogues involve N-substituted piperazines and carbamoyl imidazole tetrahydropapaverine as starting materials. Another route for synthesizing these compounds, involving the formation of carbamoyl imidazole piperazine has also been explored. Acylation of tetrahydropapaverine followed by substitution with various piperazinyl moities afforded the acetyl tetrahydropapaverine derivatives. Variously substituted piperazines have been used to monitor the effect of electron releasing and electron withdrawing substituents upon the antispasmodic activity of the molecules. Effect of varying electron densities on the antispasmodic activity, by altering the position of these groups on the benzene ring has also been monitored. Pharmacological methods involve the in vitro antispasmodic activity studies on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, a promising compound 7, a potent muscle relaxant as compared to papaverine has been obtained.