Five Novel Taccalonolides from the Roots of the Vietnamese Plant Tacca paxiana

Chemical investigation of the roots of the Vietnamese plant Tacca paxiana resulted in the isolation of five new steroidal compounds, taccalonolide R ( 6 ), S ( 7 ), T ( 8 ), U ( 9 ), and V ( 10 ). Their structures were established on the basis of NMR and mass‐spectral data. In addition, the five known taccalonolides A ( 1 ), B ( 2 ), E ( 3 ), K ( 4 ), and N ( 5 ) were also isolated and identified.     

Effect of solvent nature on spin exchange in rigid nitroxide biradicals

Intramolecular electron spin exchange as a function of temperature and solvent viscosity and polarity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two rigid nitroxide biradicals existing in one spatial conformation only. Temperature variations of the isotropic hyperfine splitting constanta and exchange integral value |J/a| were measured from EPR spectra and subsequently analyzed. The interaction of polar solvent molecules with >N-O fragments of nitroxide groups led to a slight decrease of the |J/a| value with the increase of temperatureT. In contrast, the interaction of polar solvent molecules with functional groups inside the bridge resulted in a noticeable increase of |J/a| vs.T. In the last case, a coverse relationship between the values of |J/a| and the hyperfine splitting constanta has been observed for solvents with different polarity.     

Some New Results on Key Distribution Patterns and Broadcast Encryption

This paper concerns methods by which a trusted authority can distribute keys and/or broadcast a message over a network, so that each member of a privileged subset of users can compute a specified key or decrypt the broadcast message. Moreover, this is done in such a way that no coalition is able to recover any information on a key or broadcast message they are not supposed to know. The problems are studied using the tools of information theory, so the security provided is unconditional (i.e., not based on any computational assumption).In a recent paper st95a, Stinson described a method of constructing key predistribution schemes by combining Mitchell-Piper key distribution patterns with resilient functions; and also presented a construction method for broadcast encryption schemes that combines Fiat-Naor key predistribution schemes with ideal secret sharing schemes. In this paper, we further pursue these two themes, providing several nice applications of these techniques by using combinatorial structures such as orthogonal arrays, perpendicular arrays, Steiner systems and universal hash families.     

Reactions de photoaddition de benzo[b]selenophenes avec l'acetylene dicarboxylate de methyle et avec le dichloro-1,2 ethylene

Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 $\text{kcal}\text{mole}$) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans.     

3-(Triethoxysilyl)propionitrile sol-gel coating

3-(Triethoxysilyl)propionitrile (TESPN) sol-gel has been prepared under different conditions. It was employed for coating the surfaces of quartz and aluminum. Infrared (IR) and Raman spectra of TESPN and TESPN sol-gels have been recorded in the study of the sol-gel process. Transmission and reflection absorption IR (RAIR) spectra of TESPN sol-gel coated quartz and aluminum have also been collected for better understanding the film formation on the substrate surfaces. Spectra collected at different temperatures indicated that the silane film on quartz decomposes at 700 degrees C. Results from thermal gravimetric analysis (TGA) supported this result. Based on the group frequencies and the spectral behavior in different states, some vibrational modes were assigned to the observed bands. The anticorrosion behavior of the sol-gel coated aluminum in comparison with the uncoated metal was evaluated by measuring the potentiodynamic polarization and electrochemical impedance spectra (EIS).     

A mild deprotection strategy for allyl-protecting groups and its implications in sequence specific dendrimer synthesis

A mild deprotection strategy for allyl ethers under basic conditions in the presence of a palladium catalyst is described. Under these conditions, aryl allyl ethers can be cleaved selectively in the presence of alkyl allyl ethers. These conditions are also effective in the deprotection of allyloxycarbonyl groups. The utility of the current methodology in sequence specific dendrimer synthesis is demonstrated.     

Reactivity of DNA guanyl radicals with phenolate anions

Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair.