Characterization of Silicate Complexes in Aqueous Sodium Sulfate Solutions by FAB-MS

When the sodium ion (Na⁺) concentration is increased above 0.5 mol-dm⁻³ (M), the concentrations of dissolved silica in aqueous sodium chloride (NaCl) and sodium nitrate (NaNO₃) solutions decrease because of the salting out effect. On the other hand, the concentration of the dissolved silica in aqueous sodium sulfate (Na₂SO₄) solutions increases monotonously as the concentration of Na⁺ is increased above 0.5 M. The purpose of this study is to determine the reasons why the salting-out effect is not observed in Na₂SO₄ solutions. FAB-MS (Fast Atom Bombardment Mass Spectrometry) was used to sample directly the silica species dissolved in aqueous Na₂SO₄, NaCl, and NaNO₃ solutions. In the FAB-MS spectra of these solutions, the peak intensity ratios of the linear tetramer to the cyclic tetramer largely increased for Na⁺ concentrations between (0.1 and 1) M. This shows that some characteristics of the Na₂SO₄ solutions are similar to those of the NaCl and NaNO₃ solutions. In Na₂SO₄ solutions, however, when the concentration of Na⁺ is higher than 1 M, the peak intensity of the dimer is much higher than those of the other silicate complexes. In Na₂SO₄ solutions, the SO₄²⁻ ion undergoes partial hydrolysis to form HSO⁻₄ and OH⁻ is produced. In particular, in the range where the concentration of SO₄²⁻ is high, the pH of the solution increases slightly. This higher pH yields more dimers from the hydrolysis of silicate complexes. This increase in dimer production agrees with the observation that silica dissolves in sodium hydroxide (NaOH) solutions mainly as a dimer when the concentration of NaOH is less than 0.1 M. In Na₂SO₄ solutions at high concentrations, a salting-out effect is not observed for silica. This is due to the increase in the concentration of OH⁻, which accelerates the hydrolysis of silica and results in dimer formation.     

An automatic method for the determination of carcinogenic 1-nitropyrene in extracts from automobile exhaust particulate matter

An automatic method for the determination of carcinogenic 1-nitropyrene in extracts from automobile exhaust particulate matter has been developed. Organic matter was extracted from particulate matter and the extract was concentrated. Then the extract was injected into a two-dimensional (2D) high-performance liquid chromatograph (HPLC) with a fluorescence detection system. To improve the sensitivity a large sample volume (300 microl) was applied to the HPLC system using the double on-column focusing technique. To achieve full automation and high selectivity a reduction column packed with platinum black was introduced after the 2D HPLC system using a C18 column as the primary column and a pentabromobenzyl column as the secondary column. This HPLC system could determine 0.01-3,000 ng ml(-1) of 1-nitropyrene in an extract from diesel and gasoline exhaust particulate matter at 40 min intervals.     

Tomato new sapogenols, isoesculeogenin A and esculeogenin B

Two novel sapogenols, isoesculeogenin A (1) and esculeogenin B (2) of steroidal alkaloid glycosides, lycoperoside F and esculeoside B, respectively, isolated from the ripe tomato have been characterized as (5alpha,22R,23R,25S)-3beta,23,27-trihydroxyspirosolane and (5alpha,22S,23R,25S)-22,26-epimino-16beta,23-epoxy-3beta,23,27-trihydroxycholestane, respectively.     

Light scattering of polyaniline films responding to electrochemical switching

When a laser with 543, 668 or 790±50 nm was used to irradiate the reduced polyaniline film on an indium tin oxide electrode in hydrochloric acid, the light was scattered in all directions. The intensity of the scattered light decreased with increase in the detection angle up to the right angle. When the electrode potential was scanned between the insulating and the conducting domain, the intensity varied sigmoidally with hysteresis. The intensity increased with a decrease in the absorbance. The scattering of the light can be ascribed to multiple reflection, luminescence, or Rayleigh scattering. The spectra of the scattered light was identical with that of the incident light, suggesting the absence of luminescence. The intensity increased with an increase in thickness of the film, indicating a negligible contribution of multiple reflection. Since the volume of the oxidized film is larger than that of the reduced one, the film synthesized in the oxidized state is deformed by the electrode reduction. Then, the film density becomes locally inhomogeneous and this may give rise to the Rayleigh scattering. The potential-variation of the light scattering occurred at a more negative potential than that of the absorbance at 310 nm and of the current did.     

Recovery process of respiratory muscle strength in patients following stroke: A Pilot Study

Objective: To determine the recovery process of respiratory muscle strength during 3 months following stroke, and to investigate the association of change in respiratory muscle strength and physical functions. Additionally, we compared respiratory muscle strength with those of healthy subjects. Method: In this prospective, observational study, 19 stroke patients and 19 healthy subjects were enrolled. Maximal inspiratory pressure (MIP), maximal expiratory pressure (MEP), motricity index, trunk control test, 6-minute walk test (6MWT) and functional independence measure were assessed at 1, 2, and 3 months from stroke onset in stroke patients. MIP and MEP were assessed at arbitrary times in healthy subjects. Repeated one-way analysis of variance with Bonferroni post-hoc test was used to compare the change in respiratory muscle strength in each period in stroke patients. Pearson''s correlation coefficient was computed for changes in respiratory muscle strength and physical functions. Student''s t-test was used to compare respiratory muscle strength between stroke patients at 3 months from onset and healthy subjects. Results: MIP was significantly increased at 3 months compared to 1 month. MEP was significantly increased in 2 months and 3 months, compared to 1 month. MIP changes associated with 6MWT changes. Compared to healthy subjects, MIP and MEP at 3 months were significantly lower in stroke patients. Conclusion: Respiratory muscle strength significantly increased during 3 months following stroke. However, the trend of recovery may be different. MIP changes may associated with walking endurance changes. During 3 months following stroke, respiratory muscle strength did not recover to healthy subjects.     

Flavin catalyzed oxidations of sulfides and amines with molecular oxygen

Novel biomimetic, aerobic oxidation with an organocatalyst was performed. The oxidations of organic substrates such as sulfides, secondary amines, N-hydroxylamines, and tertiary amines with molecular oxygen (1 atm) or even in air in the presence of 5-ethyl-3-methyllumiflavinium perchlorate catalyst and hydrazine monohydrate in 2,2,2-trifluoroethanol occur highly efficiently to give the corresponding oxidized compounds in excellent yields along with water and molecular nitrogen, which are environmentally benign. The TON of the oxidation of sulfides amounts to 19 000.     

Mutasynthesis of enterocin and wailupemycin analogues

Inactivation of the novel phenylalanine ammonia lyase gene encP, whose product is a key component in the biosynthetic pathway to benzoyl-coenzyme A (CoA) in the bacterium Streptomyces maritimus, resulted in the loss of production of the benzoate-primed polyketides enterocin and wailupemycin G. A series of cinnamate and benzoate derivatives were administered to the DeltaencP mutant, resulting in the formation of novel analogues bearing p-fluorobenzoate, 2- and 3-thiophenecarboxylate, and cyclohex-1-enecarboxylate residues. Given that the benzoate:CoA ligase EncN was evaluated to have broad in vitro substrate specificity towards aryl acids, the strict starter unit specificity observed in vivo indicates that the enterocin type II polyketide synthase (PKS) exerts selective control over the choice of starter units. This study represents the first mutasynthesis experiments with iterative type II PKSs.     

Perylene-tetrapalladium sandwich complexes

Bis-perylene-tetrapalladium sandwich complexes are synthesized and structurally characterized. These are the first examples of bis-arene sandwich complexes having metal-metal bond chains. X-ray crystallographic analyses showed that the tetrapalladium chain is bound to perylene ligands at the C8 edge position.