Facile preparation of an α-Keggin-type [H3W12O40] complex: Does it exist in aqueous solution?

The formation processes of α-Keggin-type [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻ complexes were investigated in aqueous W^VI (0.05–0.50 M) solutions. The formation of [H₂W₁₂O₄₀]⁶⁻ was ascertained by the appearance of a ¹⁸³W NMR line at −117 ppm, but no evidence was found for the existence of [H₃W₁₂O₄₀]⁵⁻ in the solution at the accessible pH range. The addition of (CH₃)₄N⁺ (Me₄N⁺) to the W^VI solution directly precipitated the (Me₄N)₆[H₂W₁₂O₄₀] salt. On the other hand, the addition of the larger Bu₄N⁺ cation precipitates the (Bu₄N)_4.5H_0.5[H₃W₁₂O₄₀] salt, because a naked proton formed during the crystallization process or in the solid state may enter into the Keggin shell to produce [H₃W₁₂O₄₀]⁵⁻. This explanation is based on the fact that [H₂W₁₂O₄₀]⁶⁻ is not spontaneously converted into [H₃W₁₂O₄₀]⁵⁻ in acidified aqueous solution. On the basis of their voltammetric properties, a simple diagnostic criterion was developed to distinguish between [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻.     

2'-O,4'-C-aminomethylene-bridged nucleic acid modification with enhancement of nuclease resistance promotes pyrimidine motif triplex nucleic acid formation at physiological pH

Due to the instability of pyrimidine motif triplex DNA at physiological pH, triplex stabilization at physiological pH is crucial in improving its potential in various triplex-formation-based strategies in vivo, such as gene expression regulation, genomic DNA mapping, and gene-targeted mutagenesis. To this end, we investigated the thermodynamic and kinetic effects of our previously reported chemical modification, 2'-O,4'-C-aminomethylene-bridged nucleic acid (2',4'-BNA(NC)) modification of triplex-forming oligonucleotide (TFO), on triplex formation at physiological pH. The thermodynamic analyses indicated that the 2',4'-BNA(NC) modification of TFO increased the binding constant of the triplex formation at physiological pH by more than 10-fold. The number and position of the 2',4'-BNA(NC) modification in TFO did not significantly affect the magnitude of the increase in the binding constant. The consideration of the observed thermodynamic parameters suggested that the increased rigidity and the increased degree of hydration of the 2',4'-BNA(NC)-modified TFO in the free state relative to the unmodified TFO may enable the significant increase in the binding constant. Kinetic data demonstrated that the observed increase in the binding constant by the 2',4'-BNA(NC) modification resulted mainly from the considerable decrease in the dissociation rate constant. The TFO stability in human serum showed that the 2',4'-BNA(NC) modification significantly increased the nuclease resistance of TFO. Our results support the idea that the 2',4'-BNA(NC) modification of TFO could be a key chemical modification to achieve higher binding affinity and higher nuclease resistance in the triplex formation under physiological conditions, and may lead to progress in various triplex-formation-based strategies in vivo.     

Synthesis and spectral properties of polymethine-cyanine dye-nitroxide radical hybrid compounds for use as fluorescence probes to monitor reducing species and radicals

Various hybrid compounds comprised of two types of nitroxide radicals and either a pentamethine (Cy5) or trimethine cyanine (Cy3) were synthesized. The nitroxide radicals were linked either via an ester-bond to one or two N-alkyl carboxyl-terminated groups of Cy5, or via two amido-bonds (aminocarbonyl or carbonylamino group) to the 5-position of the indolenine moieties of Cy5 and Cy3. Changes in fluorescence and ESR intensities of the hybrid compounds were measured before and after addition of Na ascorbate in PBS (pH 7.0) to reduce the radicals. Among the hybrid compounds synthesized, those that linked the nitroxide radicals via an aminocarbonyl residue at the 5-position of the indolenine moieties on Cy5 and Cy3 exhibited a 1.8- and 5.1-fold increase in fluorescence intensity with the reduction of the nitroxide segment by the addition of Na ascorbate, respectively. In contrast, fluorescence intensity was not enhanced in the other hybrid compounds. Thus, the hybrid compounds which exhibited an increase in fluorescent intensity with radical reduction can be used in the quantitative measurement of reducing species such as Fe(2+) and ascorbic acid, and hydroxyl radicals. Because these hybrid compounds have the advantage of fluorescing at longer wavelengths-661 (Cy5) or 568 (Cy3)nm, respectively, they can be used to measure radical-reducing species or radicals either in solution or in vivo.     

Synthesis and evaluation of new caged compound with thiochromone derivative

A new caged firefly luciferin (luciferin) with a thiochromone S,S-dioxide (TSSDO) as a photolabile protecting group was synthesized. Photodeprotection of the caged compound proceeded smoothly under photoirradiation at 365 nm in aqueous solution. The bioluminescence of the regenerated luciferin after uncaging was detected using a typical luciferin–luciferase reaction. These results indicated that TSSDO could be an attractive chemical tool for regulating biological phenomena.     

Microbial degradation of physiologically active peptides by strain B-9

The reaction of some physiologically active peptides with bacterial strain B-9 has been investigated. Bradykinin, β-endorphin, and [Leu(5)]enkephalin were quickly degraded, with half-lives of <5 min. Somatostatin, substance P, and angiotensin I were degraded relatively smoothly, with half-lives of 10 min to 1 h, whereas oxytocin and insulin were slowly degraded, with half-lives of 1 and 4 days, respectively. Vasopressin was barely degraded, with a half-life of >7 days. Linearized vasopressin, prepared by the reductive cleavage of the disulfide bond followed by alkylation with iodoacetamide, was degraded significantly faster than intact vasopressin, with a half-life of 2.5 h. A loop formed by disulfide bond formation was regarded as one of the degradation-resistant factors. Hydrolysis of the peptides in this study took place through cleavage of various peptide bonds, and the strain B-9 may bear similarities to the neutral endopeptidase in terms of its broad selectivity.     

Is nitric oxide (NO) an antioxidant or a prooxidant for lipid peroxidation?

Antioxidant and prooxidant effects of nitric oxide (NO) on lipid peroxidation in aqueous and non-aqueous media were examined. In an aqueous solution, NO did not induce peroxidation of unoxidized methyl linoleate (ML) and suppressed the radical initiator-induced oxidation of ML. NO suppressed the Fe(II) ion-induced oxidation of mouse liver microsomes. NO reduced the O2 consumption during the radical initiator-induced oxidation of linoleic acid in an aqueous medium. NO conversion into NO2- in an aqueous medium was not affected by unoxidized ML and was slightly reduced by peroxidizing ML. On the other hand, as well as pure NO2, NO induced peroxidation of unoxidized ML in n-hexane in a dose-dependent fashion. NO did not suppress the radical initiator-induced oxidation of ML in n-hexane. Nitrogen oxide species (NO2 or N2O3) formed by autoxidation was dramatically lost in n-hexane in the presence of unoxidized ML. The results indicated that NO terminated lipid peroxidation in an aqueous medium, whereas NO induced lipid peroxidatiton in a non-aqueous medium. Hence, NO showed both antioxidant and prooxidant effects on lipid peroxidation depending on the solvents.     

A novel synthesis of (±)-descarboxyquadrone

The novel synthesis of descarboxyquadrone (3) and its model compound (4) by using the acid-catalyzed rearrangement of [4.3.2]propellanones is described.     

Inflection points and topology of surfaces in 4-space

We consider asymptotic line fields on generic surfaces in 4-space and show that they are globally defined on locally convex surfaces, and their singularities are the inflection points of the surface. As a consequence of the generalized Poincaré-Hopf formula, we obtain some relations between the number of inflection points in a generic surface and its Euler number. In particular, it follows that any 2-sphere, generically embedded as a locally convex surface in 4-space, has at least 4 inflection points.

     

Investigation for a Drastic Change of the Core in 23O and 24O

We study the radius and energies of oxygen isotopes towards the neutron drip-line. The abrupt increase of the radius at ²³O is investigated with two different approaches; the m-scheme cluster-orbital shell model (COSM) and a simplified model approach with the core plus one and two valence neutrons. We investigate properties of the oxygen isotopes by changing the radius of the ¹⁶O-core in the m-scheme COSM approach and obtain the result that the broad structure of ¹⁶O is favored in the ²³O and ²⁴O. In the simplified model approach, we estimate the magnitude of the change of the size of ²²O in ²³O and ²⁴O.