Stereospecific substitution of enantiomerically pure 1-(2-pyridinyl)ethyl methanesulfonate with beta-dicarbony compounds

The alkylation of the sodium salt of the malonic acid diester with (R)-1-(2-pyridinyl)ethyl methanesulfonate (2) gave the dimethyl (R)-[1-(2-pyridinyl)ethyl]malonate (3a), stereospecifically. The alkylation reaction of methyl acetoacetate gave the methyl (2'S,2R/2S)-3-oxo-2-[1-(2-pyridinyl)ethyl]butanoate (3d) along with the methyl (S)-3-[1-(2-pyridinyl)ethoxy]-2-butenoate (4d). The acid hydrolysis and decarboxylation of 3d under acidic conditions gave (R)-4-(2-pyridinyl)pentan-2-one (6), and the alkylation of methyl (R)-[1-(2-pyridinyl)ethyl]acetoacetate with benzyl bromide gave a mixture of C-benzylated and O-benzylated products 7 and 8.     

Diels‐alder reaction of 1‐methyl‐3,6,8‐trinitro‐2‐quinolone

1‐Methyl‐3,6,8‐trinitro‐2‐quinolone (1) behaved as the dienophile in Diels‐Alder reactions with dienes. When cyclopentadiene was used, cycloadduct 4 was obtained, which was then aromatized on treatment with triethylamine. In the reaction of 1 with hydrazone of 2‐butenal, phenanthridine derivative 7 was produced.     

A single-chain magnet formed by a twisted arrangement of ions with easy-plane magnetic anisotropy

A unique "single-chain quantum magnet" was formed by an alternating arrangement of high-spin FeII/low-spin FeIII ions. Although the predominant spin-carrier components (high-spin FeII) possess easy-plane magnetic anisotropy (D > 0), twisted arrangement of easy-planes along the chain axis defines a novel class of one-dimensional Ising system.     

Gas chromatographic/mass spectrometric determination of benzene and its alkyl derivatives in indoor and outdoor air in Fuji, Japan

An analytical method was established for the determination of benzene and 13 of its alkyl derivatives. The method was applied to a survey of indoor pollution that investigated the usefulness of the method, concentration levels, seasonal variations, profiles, correlations between compounds, and factors that affected indoor pollution by these compounds. The survey was performed in 21 houses in the summer of 1999 and 20 houses in the winter of 1999-2000 in Fuji, Japan. All the target compounds were detected in the indoor and outdoor air of all houses. Outdoor concentrations of benzene ranged from 0.779 to 3.17 microg/m3 in summer and from 1.35 to 6.04 microg/m3 in winter, whereas indoor concentrations of benzene ranged from 0.694 to 3.11 microg/m3 in summer and from 1.65 to 6.89 microg/m3 in winter. Indoor concentrations of the target compounds, except for benzene, were elevated, compared with outdoor concentrations. Because indoor and outdoor concentrations of benzene and its derivatives in summer were lower than in winter, the emission of these compounds may be increased by use of a heater and other variables present in winter. Profiles of the compounds, correlations between the compounds, and factors that affected indoor pollution (determined by multiple regression analysis) were investigated. These results suggested that indoor benzene predominantly penetrated from outdoors and that other benzene derivatives were emitted from indoor sources, such as paint solvents and kerosene heaters.     

Computational assignment of the EC numbers for genomic-scale analysis of enzymatic reactions

The EC (Enzyme Commission) numbers represent a hierarchical classification of enzymatic reactions, but they are also commonly utilized as identifiers of enzymes or enzyme genes in the analysis of complete genomes. This duality of the EC numbers makes it possible to link the genomic repertoire of enzyme genes to the chemical repertoire of metabolic pathways, the process called metabolic reconstruction. Unfortunately, there are numerous reactions known to be present in various pathways, but they will never get EC numbers because the EC number assignment requires published articles on full characterization of enzymes. Here we report a computerized method to automatically assign the EC numbers up to the sub-subclasses, i.e., without the fourth serial number for substrate specificity, given pairs of substrates and products. The method is based on a new classification scheme of enzymatic reactions, named the RC (reaction classification) number. Each reaction in the current dataset of the EC numbers is first decomposed into reactant pairs. Each pair is then structurally aligned to identify the reaction center, the matched region, and the difference region. The RC number represents the conversion patterns of atom types in these three regions. We examined the correspondence between computationally assigned RC numbers and manually assigned EC numbers by the jackknife cross-validation test and found that the EC sub-subclasses could be assigned with the accuracy of about 90%. Furthermore, we examined the correlation with genomic information as represented by the KEGG ortholog clusters (OC) and confirmed that the RC numbers are correlated not only with elementary reaction mechanisms but also with protein families.     

Photocatalytic activity of SrTiO3 codoped with nitrogen and lanthanum under visible light illumination

Yellow SrTiO3 powders codoped with nitrogen and lanthanum (STO:N,La) were studied as visible light photocatalysts. The crystal phase of STO:N,La exhibited a pure perovskite phase, and O and Sr sites atoms were substitutionally doped with N and La atoms, respectively. The first principle calculation of STO:N,La indicated that the edge of the N(2p) band is situated above the valence band, which consisted of O(2p) orbitals, and the La orbitals did not exist in the band gap of SrTiO3. STO:N,La exhibited a higher oxidation activity of gaseous 2-propanol under vis illumination than SrTiO3 doped only with nitrogen (STO:N). The high activity of STO:N,La was due to the decrease in the oxygen vacancies, which acted as electron-hole recombination centers, because codoping with La3+ and N3- ions maintained the charge balance. The optimum doping density of N and La for visible light activity was 0.5%, and STO:N,La(0.5%) had an activity under UV illumination similar to pure SrTiO3.     

Spin and fluorescence label studies on bile salt micelles

The interior structure of micelles formed by bile salts, which differ in the number and location of the hydroxyl groups attached to the steroid nucleus, was studied by the spin label and fluorescence label methods. The results show that the interior structure of micelles formed by bile salts possessing two hydroxyl groups is more rigid than that of micelles formed by trihydroxy bile salts regardless of the terminal hydrophilic group. Even in the case of dihydroxy bile salts possessing two hydroxyl groups in the same location, the interior structures of their micelles are different from each other depending on the orientation of their hydroxyl groups. It is considered that hydroxyl groups as well as the terminal hydrophilic group play an important role in the micellar formation of bile salts.     

Biomonitoring of environmental pollution based on studies of trace elements in soil and crops

Most elemental concentrations in crops should be related to those in soil and other circumferential environments. In the present study, more than thirty minor and trace elements in soils and crops were determined by the use of ICP, XRF and NAA. Soil and crop samples were collected at eleven abandoned mine regions in Chungnam province located in the middle part of Korea. The elemental concentrations in soils were compared to the crustal mean concentrations in both Chungnam area and worldwide. The concentration ratios of the elements in soils and crop compartments were calculated and the distribution characteristics of each element were investigated between soil and crop compartments.     

Photocrosslinking of polymers bearing epoxy or epithio groups by quinones in the solid state

Photocrosslinking of poly(glycidyl methacrylate) (PGMA) and a copolymer of 2,3-epithiopropyl methacrylate and methyl methacrylate [P(ETMA-co-MMA)] was studied in the solid state in the presence of various quinones. The efficiency of photocrosslinking was strongly dependent upon the structures of quinones and the kinds of polymers. For example, the alkyl-substituted quinones such as 2-ethyl-p-benzoquinone (EQ), 2-tert-butyl-p-benzoquinone (tBQ) and 2,5-di-tert-butyl-p-benzoquinone (2,5-dtBQ) did not induce photocrosslinking of poly(methyl methacrylate) (PMMA), whereas they acted as efficient photocrosslinking agents in PGMA and P(ETMA-co-MMA). The formation of charge transfer complexes did not play a principal role in this effective photocrosslinking, because the order of the photocrosslinking efficiency [EQ > tBQ > 2,5-dtBQ > p-benzoquinone (Q)] was not in agreement with that of the magnitude of the electron affinities of quinones, i.e., Q > EQ > tBQ > 2,5-dtBQ. Photopolymerization of propylene sulfide (PS) in the presence of tBQ or Q was also investigated. The presence of tBQ induced polymerization of PS upon UV irradiation. From these results, it was deduced that the photocrosslinking of P(ETMA-co-MMA) film containing tBQ proceeds via a cationic polymerization of epithio groups. A similar mechanism should be applicable to the photocrosslinking of PGMA film containing tBQ.