Nitrosation of Phenolic Substrates under Mildly Basic Conditions: Selective Preparation of p-Quinone Monooximes and Their Antiviral Activities

Nitrosation of 3-methoxyphenol and 1-naphthol were examined under both acidic (NaNO(2)-EtCO(2)H-H(2)O) and basic (i-AmNO(2)-K(2)CO(3)-DMF) conditions. Acidic nitrosations afforded ortho-directed products, whereas para-directed nitrosations were observed under basic conditions to yield p-quinone monooximes. The basic para-directed nitrosation was further examined using 15 phenols, two naphthols, and four phenolic heterocyclics. A one-pot operation of the basic nitrosation followed by methylation with dimethyl sulfate gave the corresponding methyl ethers in high yield. Two p-quinone monooximes derived from 3-methoxyphenol and 8-hydroxyquinoline showed a moderate activity against HSV-1, and the latter oxime was also effective against HSV-2. On the other hand, p-quinone monooximes derived from methyl salicylate, 1-naphthol, 7-hydroxy-2-methylbenzo[b]furan, and 8-hydroxycoumarin showed the comparable activity to that of DDI against HIV-1.     

A large deviation principle for (r,p)-capacities on the Wiener space

Summary We formulate and prove a large deviation principle for the (r, p)-capacity on an abstract Wiener space. As an application, we obtain a sharpening of Strassen's law of the iterated logarithm in terms of the capacity.     

NAD(P)+-NAD(P)H models. 90. Stereoselection controlled by electronic effect of a carbonyl group in oxidation of NAD(P)H analog

4-Monodeuterated NAD(P)H model compounds (1,4,6,7-tetrahydro-1,6,11-trimethyl-5-oxo-5H-benzo[c]pyrido[2,3-e]az epin; 11Me-MMPAH) have been oxidized with a series of p-benzoquinone and its derivatives in the presence of Mg2+. The models have an axial chirality with respect to the orientation of carbonyl dipole, the dihedral angle of which is larger than 55 degrees out of the plane of dihydropyridine ring. Without Mg2+, the anti- (with respect to the carbonyl dipole) hydrogen is 3 to 32 times more reactive than the corresponding syn-hydrogen, whereas, when Mg2+ is present in the system, the selectivity is shifted toward the syn-preferency. Mg2+ plays the role of a Lewis acid catalyst to control the stereochemistry at the same time as it catalyzes the reaction.     

Leaching behavior of metal-containing species in residual oils with different organic solvents

The leaching behavior of two different residual oils is investigated with 24 organic solvents including alkanes, aromatics, esters, ethers ketones, alcohols and nitrogen compounds. A 2-g portion of sample oil is shaken with 20 ml of the organic solvent. The leaching of the organic matrix of the oil is determined by weighing the dissolved organic matrix after removal of solvent. The leaching of vanadium, iron and nickel was determined by flame atomic absorption spectrophotometry after ashing of the dissolved fraction. The leaching of those metals depends strongly on the solvent used; for example, vanadine is almost completely leached into toluene, but only slightly into methanol. The leaching of iron is poor compared with that of vanadium or nickel. In most solvents, leaching of those metal-containing species is poorer than that of organic material. Exceptionally, N,N-dimethylformamide is more efficient in leaching vanadium species than organic material.     

Coprecipitation with metal hydroxides for the determination of beryllium in seawater by graphite furnace atomic absorption spectrometry

Coprecipitation first with magnesium hydroxide, next with tin(IV) hydroxide is developed for the determination of traces of beryllium in sea-water. To a 200-ml sample is added a sodium hydroxide solution to form magnesium hydroxide at pH 11.5, on which beryllium is quantitatively coprecipitated. The precipitate is separated by centrifugation and dissolved in 2 ml of 12 mol/l hydrochloric acid. The resulting solution (ca. 10 ml) is mixed with 2 mg of tin (IV) carrier and the pH is adjusted to 5.0 to collect the beryllium on tin (IV) hydroxide, leaving magnesium ions in the solution. The tin (IV) hydroxide is centrifuged, dissolved in 0.1 ml of 5 mol/l hydrobromic acid, and then diluted to 1 ml with water. Magnesium is so added as to be 500 g/ml for increasing the sensitivity about four times, and the beryllium in the solution is determined by graphite furnace atomic absorption spectrometry. The experiments with synthetic seawater samples showed that pg — g amounts of beryllium can be coprecipitated on the metal hydroxides and beryllium at the low ng/1 level can be determined with reasonable precision (RSD < 10%). The detection limit of the proposed method is 0.5 ng/l of beryllium in seawater.     

Involvement of human small fragment nuclease in the resistance of human cells to UV-C-induced cell death

Human small fragment nuclease (Sfn) is one of the cellular proteins that were reported to degrade small, single-stranded DNA and RNA. However, the biological role of Sfn in cellular response to various stressors such as UV-C (mainly 254 nm wavelength ultraviolet ray) remains unclear. We have examined whether modulation of human SFN gene expression affects cell survival capacity against UV-C-induced cell death, analyzing colony survival ability in UV-C-sensitive human RSa cells treated with short double-stranded RNA (siRNA) specific for SFN messenger RNA (mRNA). The expression levels of SFN mRNA in the siRNA-treated RSa cells decreased to about 15% compared with those in the control siRNA-treated cells. The siRNA-treated RSa cells showed lower colony survival and higher activity of caspase-3 after UV-C irradiation than the control siRNA-treated RSa cells. Furthermore, the removal capacity of cyclobutane pyrimidine dimers (CPD) in the siRNA-treated RSa cells decreased compared with the control siRNA-treated RSa cells. There was no difference in the colony survival and CPD removal capacity after UV-C irradiation between the control siRNA-treated RSa cells and mock-treated RSa cells. These results suggest that SFN expression is involved in resistance of RSa cells to UV-C-induced cell death through the roles it plays in the DNA repair process.     

Synthetic approach toward antibiotic tunicamycins — VI total synthesis of tunicamycins

Tunicamycins and their eight analogs have been synthesized by condensation of a N-acetyl-D-glucosamine derivative and an anomeric chloride of tunicaminyl uracil, followed by deprotections and N-acylation.     

Facile routes to natural acyclic polyenes syntheses of spilanthol and trail pheromone for termite

The synthetic procedures for spilanthol and trail-following pheromone for a southern subterranean termite were described. The syntheses heavily depend on the new diene synthesis using titanium reagent.     

Chromatographic molecular recognition for catechol-related compounds using thiacalix[4]arene as an effective selector

Thiacalix[4]arene (5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathiacalix[4]arene) is an amphiphilic molecule comprising four p-tert-butylphenol-like groups ortho-linked by single sulfur atoms. This molecule has a high electron density area owing to the close proximity of the hydroxyl groups and sulfur atoms. We studied the applicability of this interesting compound as a selector for high-performance liquid chromatography (HPLC) thereby presumably exploiting this feature. Firstly, uniformly sized polymer particles were prepared by using a multi-step swelling and polymerization method with ethylene glycol dimethacrylate (EDMA) as a cross-linker. Methacrylic acid (MAA) was introduced onto the surface of the resulting polymer particles through a new modification method. Thiacalix[4]arene was chemically bonded through the MAA group by using 1,4-dibromobutane as a spacer to reduce steric hindrance around the MAA and the polymer particle itself. The performance of the prepared polymer-based thiacalix[4]arene-modified stationary phase was evaluated with HPLC. Specific chromatographic retention behavior was observed for catechol relative to positional isomers of xylene, cresol, and benzene-diol. Catecholamine and catechol showed specific chromatographic retention behavior.