Spectrophotometric determination of traces of hydrogen peroxide with the Ti(IV)-xylenol orange and the Ti(IV)-chromazurol S reagents

The formation of mixed ligand complexes in Ti(IV)-xylenol orange (XO)-H₂O₂ and Ti(IV)-chromazurol S (CAS)-H₂O₂ systems was studied by spectrophotometry. The former system gave constant absorbance (λ_max = 562 nm) under the condition of [XO]/[Ti(IV)] = 1 in the pH 2–4 region. In the latter system, a distinct maximum at 557 nm was observed when [CAS]/[Ti(IV)] = 4 in the pH range of 4.5–5.2. In both cases, the absorbance at λ_max was stable for a long time and proportional to the concentration of hydrogen peroxide. From those facts, the usefulness of the mixtures of Ti(IV)-XO and Ti(IV)-CAS as the colorimetric reagents for the determination of hydrogen peroxide can be expected. The conditions for the use of the Ti(IV)-XO and the Ti(IV)-CAS reagents were examined in detail, and both reagents were found to be available for trace analysis of hydrogen peroxide with high sensitivity.     

Synthesis of block copolymer with polystyrene and nylon units

Bis-ε-aminocaproylaminocaproylhexamethylenediamine ( I ) was synthesized as an analog of 6-nylon pentamer diamine, and its incorporation into block copolymers was studied with the use of α,ω-dihydroxyl, α,ω-bisdimethylchlorosilyl, and α,ω-diepoxy polystyrene. In the course of the experiments, the stability and the reactivity of 4,4′-diphenylmethane diisocyanate and tetramethylene diisocyanate in aprotic dipolar solvents were examined by infrared spectroscopy. The only usable solvent, N-methylpyrrolidone, was found still inadequate for the synthesis involving I, diisocyanate, and α,ω-dihydroxyl polystyrene. A block copolymer having M _n = 18,000 was obtained by the reaction of I and α,ω-diepoxy polystyrene. All T_g values of the block copolymers were above 90°C, higher than for polystyrenes with corresponding molecular weight.     

Studies on reactions of the N-phosphonium salts of pyridines. XIII. Direct polycondensation reaction of carbon dioxide or disulfide with diamines under mild conditions

Polyureas of high molecular weight were obtained by the direct polycondensation reaction of carbon dioxide with diamines at 40°C for several hours under a pressure of carbon dioxide (below 30 atm) by use of diphenyl phosphite in pyridine. Optimal temperature and pressure were 40°C and 20 atm of carbon dioxide. The polycondensation reaction was also affected by solvents and type and amounts of tertiary amines. Pyridine was most effective as tertiary amine and solvent as well. Of the phosphorous compounds used, triaryl phosphites and diphenyl phosphite were most effective, but trialkyl phosphites failed to give polymer. The reaction was assumed to proceed via a carbamyl N-phosphonium salt of pyridine formed by dephenoxylation of phosphites. Similarly, polythioureas were prepared by heating a mixture of carbon disulfide, diamines, and diphenyl phosphite in pyridine at 40°C for 6 hr under nitrogen.     

522—Catalytic oxydation of biological components on platinum electrodes modified by adsorbed metals: Anodic oxidation of glucose

The catalytic oxidation of glucose on Pt electrodes modified by adsorbed metals was studied in 1 M HClO₄ by linear sweep voltammetry. The adsorbed metals (denoted as M_ad, such as Bi_ad and Pb_ad) formed on Pt in the potential region more positive than the reversible potential of an M⁼⁺/M^o couple, lead to a marked increase in the anodic c?urrent of glucose by about one order of magnitude. The catalytic activity depends on the surface coverage by the M_ad. The strongly adsorbed species of lactone type, which are responsible for blocking the successive oxidation, are formed on the electrode surface in the anodic processes of glucose on a bare Pt electrode. The formation of such poisonous species is accelerated in the presence of adsorbed hydrogen on Pt. The effects of M_ad were discussed on the basis that M_ad plays its major role on the Pt electrode surface in removal of the adsorbed hydrogen which initiates the formation of the poisonous species.     

Spinel, YbFe2O4, and Yb2Fe3O7 types of structures for compounds in the In2O3 and Sc2O3---A2O3---BO systems [A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn] at temperatures over 1000°C

In the Sc₂O₃---Ga₂O₃---CuO, Sc₂O₃---Ga₂O₃---ZnO, and Sc₂O₃---Al₂O₃---CuO systems, ScGaCuO₄, ScGaZnO₄, and ScAlCuO₄ with the YbFe₂O₄-type structure and Sc₂Ga₂CuO₇ with the Yb₂Fe₃O₇-type structure were obtained. In the In₂O₃---A₂O₃---BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO₄, InGaNiO₄, and InFe³⁺MgO₄ with the spinel structure, InGaZnO₄, InGaMgO₄, and InAlCuO₄ with the YbFe₂O₄-type structure, and In₂Ga₂MnO₇ and In₂Ga₂ZnO₇ with the Yb₂Fe₃O₇-type structure were obtained. InGaMnO₄ and InFe₂O₄ had both the YbFe₂O₄-type and spinel-type structures. The revised classification for the crystal structures of AB₂O₄ compounds is presented, based upon the coordination numbers of constituent A and B cations.     

Irradiation softening in mo single crystals

Temperature dependence of yield stress was studied on Mo single crystals of two orientations after neutron irradiation at low temperature. After the low temperature irradiation, the yield stresses decreased. The isochronal annealing measurements of yield stress were also performed. The yield stresses after low temperature irradiation recovered with increasing of annealing temperature.     

Stability of benzoporphyrin photosensitizers in water/ethanol mixtures: pKa determination and self‐aggregation processes

Benzoporphyrin monoacid derivatives, here named B3A and B3B, are promising new drugs for photodynamic therapy. Although both isomers show interesting characteristics as photosensitizing compounds, they have some distinct physicochemical properties such as the tendency to self‐aggregate in water‐rich media. Because pH drives the presence of each species, the pK_a of these compounds assumes strategic importance. However, traditional micro‐titration methods and UV–Vis absorption techniques fail to give reliable pK_a values due to the characteristics of this highly complex system, such as the precipitation of hydrophobic species, close pK_a values, and high absorption band superposition. In the present work, chemometric tools are employed to evaluate pK_a, and the kinetic tendency of monomers to undergo self‐aggregation is investigated. In solvent mixtures at low water percentage in ethanol, both B3A and B3B are stabilized in a monomeric state. However, in mixtures with a high water content, self‐aggregation takes place, mainly under a mild pH acid condition (3 < pH < 6), in which the prevalent protolytic species of both isomers is the neutral charged form, compounds with carboxylic and porphyrin free‐base groups. It is demonstrated that both isomers can undergo aggregation following a self‐catalytic mechanism, which is 2000 times slower to B3A than B3B. For B3A, the aggregation is manifested by a decrease in the monomer band with the aggregation band probably superposed to that of the monomer. For B3B, together with the decrease in the monomer band, a new band related to self‐aggregates is observed. Copyright © 2010 John Wiley & Sons, Ltd.     

The role of mammalian autophagy in protein metabolism

Autophagy is in principle a non-selective degradation system within cells, which is conserved in all eukaryotic cells. Autophagy is usually suppressed at low levels but can be upregulated during periods of nutrient starvation, which facilitates cell survival. In addition to this fundamental role, basal autophagy was recently revealed to be important for constitutive turnover of intracellular proteins and organelles. Autophagy has been considered to be involved also in presentation of endogenous antigens, degradation of invasive bacteria, tumor suppression, cell death and development. This review will discuss the biological significance of autophagy, particularly focusing on its implications in protein metabolism in mammals.