Nitroxyl radicals: electrochemical redox behaviour and structure-activity relationships

Comparative study of electrochemical redox behaviour of five different nitroxyl radicals leads to the direct correlation between one-electron redox potentials and group electronegativity of the beta-substituent on the ring. Beta-substituents with an electron-donating effect caused a negative shift in the one-electron oxidation and one-electron reduction potentials of the nitroxyl radicals. In a similar aspect, beta-substituents with an electron-withdrawing effect behaved oppositely.     

Frozen water phase method for logD measurement using a 96-well plate

In this study, a frozen water phase method for log D measurement using a 96-well plate was developed. In the case of log D measurement of compounds, the problem of octanol contamination often occurs; in lipophilic compounds, the concentration of the octanol phase is much higher than that of the water phase. When the water phase is separated from the octanol phase, a small amount of octanol phase contamination could strongly influence the concentration of the water phase. To avoid this problem, the frozen water phase method was developed. The water phase was frozen in liquid nitrogen and then the unfrozen octanol phase was removed. To remove the portion of the octanol remaining on the frozen water phase, the surface of the frozen water phase was washed with octanol and water/ethanol (50/50, v/v). The validity of the method was confirmed by results of commercially available drugs at the log D range from 0 to 4. Further, it was found that this method had the ability to evaluate the pH-log D profile of compounds in the range from pH 2 to pH 12. As a result, we developed the convenient and accurate method that is effective in preventing contamination with a wide dynamic range.     

Novel sample preparation technique with needle-type micro-extraction device for volatile organic compounds in indoor air samples

A novel needle-type sample preparation device was developed for the effective preconcentration of volatile organic compounds (VOCs) in indoor air before gas chromatography–mass spectrometry (GC–MS) analysis. To develop a device for extracting a wide range of VOCs typically found in indoor air, several types of particulate sorbents were tested as the extraction medium in the needle-type extraction device. To determine the content of these VOCs, air samples were collected for 30 min with the packed sorbent(s) in the extraction needle, and the extracted VOCs were thermally desorbed in a GC injection port by the direct insertion of the needle. A double-bed sorbent consisting of a needle packed with divinylbenzene and activated carbon particles exhibited excellent extraction and desorption performance and adequate extraction capacity for all the investigated VOCs. The results also clearly demonstrated that the proposed sample preparation method is a more rapid, simpler extraction/desorption technique than traditional sample preparation methods.     

Key role of chemical hardness to compare 2,2-diphenyl-1-picrylhydrazyl radical scavenging power of flavone and flavonol O-glycoside and C-glycoside derivatives

The antioxidant activities of flavonoids and their glycosides were measured with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH radical, DPPH(·)) scavenging method. The results show that free hydroxyl flavonoids are not necessarily more active than O-glycoside. Quercetin and kaempferol showed higher activity than apigenin. The C- and O-glycosides of flavonoids generally showed higher radical scavenging activity than aglycones; however, kaempferol C3-O-glycoside (astragalin) showed higher activity than kaempferol. In the radical scavenging activity of flavonoids, it was expected that OH substitutions at C3 and C5 and catechol substitution at C2 of B ring and intramolecular hydrogen bonding between OH at C5 and ketone at C3 would increase the activity; however, the reasons have yet to be clarified. We here show that the radical scavenging activities of flavonoids are controlled by their absolute hardness (η) and absolute electronegativity (χ) as a electronic state. Kaempferol and quercetin provide high radical scavenging activity since (i) OH substitutions at C3 and C5 strikingly decrease η of flavones, (ii) OH substitutions at C3 and C7 decrease χ and η of flavones, and (iii) phenol or o-catechol substitution at C2 of B ring decrease χ of flavones. The coordinate r(χ,?η) as the electron state must be small to increase the radical scavenging activity of flavonoids. The results show that chemically soft kaempferol and quercetin have higher DPPH radical scavenging activity than chemically hard genistein and daidzein.     

Gravitational sedimentation effect of colloidal silica crystals in binary systems of titanium dioxide and silica particles

Colloidal crystals can be formed of silica particles while those of titania particles are not known under the normal gravitational field, because of their high specific gravity. We found by the Kikuchi--Kossel diffraction technique that, when silica particles (diameter: D?=?170?nm; density: ρ?=?2.2?g cm^?3) are mixed with titania particles (D?=?127?nm; ρ?=?3.9?g cm^?3), colloidal crystals are formed. Colloidal crystals started out with body-centred-cubic structure and changed to face-centred-cubic structures after about 60 days. Transitions began from the bottom of the container. Thus, the transitions are considered to be due to gravitational sedimentation. It is significant that the crystal growth process, which has not been observed in one-component dispersions of the silica particles, was found using titania particles with a wide range of the practical applicability.     

Absorption spectroscopy of uranium plasma for remote isotope analysis of next-generation nuclear fuel

CdSe/Se multilayer thin films were prepared using sequential thermal evaporation technique by varying the thickness of selenium sublayers. Identifying the prominent peaks observed in the XRD spectra of the top layer CdSe which corresponds to the (100) plane with wurtzite structure, the average size of the crystallites was calculated for the CdSe nanocrystals. Experimentally measured band gaps are larger than bulk band gap of CdSe. This confirms the presence of spin-orbit splitting of energy levels. Size of the crystallites was then calculated with the theoretical prediction of the effective mass approximation model (i.e., Brus model). It resulted in that the diameters of crystallites were much smaller than the Bohr exciton diameter (11.2 nm) of CdSe. Thus the structural and optical properties of CdSe/Se multilayer thin films reveal the effect of quantum confinement of CdSe crystallites in Se matrix for various sublayer thicknesses. Confinement effect is more pronounced while sublayer thickness of selenium increases.     

A Fluorine-19 Magnetic Resonance Probe,Shiga-Y5, Downregulates Thioredoxin-Interacting Protein Expression in the Brain of a Mouse Model of Alzheimer’s Disease

Thioredoxin-interacting protein (TXNIP) is involved in multiple disease-associated functions related to oxidative stress, especially by inhibiting the anti-oxidant- and thiol-reducing activity of thioredoxin (TXN). Shiga-Y5 (SY5), a fluorine-19 magnetic resonance probe for detecting amyloid-β deposition in the brain, previously showed therapeutic effects in a mouse model of Alzheimer’s disease; however, the mechanism of action of SY5 remains unclear. SY5 passes the blood–brain barrier and then undergoes hydrolysis to produce a derivative, Shiga-Y6 (SY6), which is a TXNIP-negative regulator. Therefore, this study investigates the therapeutic role of SY5 as the prodrug of SY6 in the thioredoxin system in the brain of a mouse model of Alzheimer’s disease. The intraperitoneal injection of SY5 significantly inhibited TXNIP mRNA (p = 0.0072) and protein expression (p = 0.0143) induced in the brain of APP/PS1 mice. In contrast, the levels of TXN mRNA (p = 0.0285) and protein (p = 0.0039) in the brain of APP/PS1 mice were increased after the injection of SY5. The ratio of TXN to TXNIP, which was decreased (p = 0.0131) in the brain of APP/PS1 mice, was significantly increased (p = 0.0072) after the injection of SY5. These results suggest that SY5 acts as a prodrug of SY6 in targeting the thioredoxin system and could be a potential therapeutic compound in oxidative stress-related diseases in the brain.     

Phase transition and extended X-ray absorption fine structure of melt-spun amorphous Fe100−xYx alloys

The phase diagram and local structure of melt-spun amorphous (a-) Fe_100−xY_x (22?x?62) alloys were investigated using AC and DC magnetic and extended X-ray absorption fine structure (EXAFS) measurements. The a-Fe–Y system shows reentrant spin glass (RSG) behavior for 42?x?58 and spin glass (SG) behavior for 60?x. Two SG transition temperatures, T_g and T_f, were obtained in the RSG state. The T_g, T_f and Curie temperature T_C decrease with increasing x, and the T_C and T_g vanish at x=60. A new magnetic phase diagram for the melt-spun a-Fe_100−xY_x alloys was obtained from magnetic measurements for higher Y concentration. The magnetic states of the a-Fe_100−xY_x alloys change remarkably around x=60 and an EXAFS study revealed that the average atomic distance between nearest-neighboring Fe atoms changes at approximately x=60.     

Direct Observation of Radical Intermediates While Investigating the Redox Behavior of Thiamin Coenzyme Models

The redox behavior of “active aldehydes” 1 ⁻ derived from 3-benzylthiazolium salts and simple aldehydes in the presence of a base has been examined with low-temperature cyclic voltammetry and EPR spectroscopy. The highly negative oxidation potentials of 1 ⁻ and the spin distribution of the intermediate radicals 1 ^. indicate that the active aldehyde can act as an efficient electron mediator in thiamin-dependent enzymatic redox systems.