Characteristics of a protein error in determination of serum protein in the presence of inorganic salt.

There is a possibility that the color development of the dye-binding method based on a protein error of a pH indicator is affected by the coexisting inorganic salt. Thus, the author theoretically and experimentally investigated the effect of the inorganic salt on the protein error. In a theoretical analysis, the anion of an inorganic salt, like the dissociated dye and buffer anions, was assumed to react with the protein, forming a colorless anion-protein complex. The calculated results were compared with those obtained by experiments using three pH indicators and various kinds of inorganic salts. The calculated results obtained are as follows: (1) The color development decreases with increasing the concentration of the inorganic salt and the equilibrium constant of the reaction between the inorganic salt and protein; (2) The rate of the absorbance decrease is larger for a lower concentration of the inorganic salt than for a higher one; (3) The larger is the equilibrium constant, the larger is the absorbance decrease. The absorbance decrease was caused by the anion, and was increased by increasing the anion concentration. The magnitude of the effect of the anion was iodide > bromide > chloride, which was associated with their ionic radius. The difference in the effect of the anion was thought to indicate that the equilibrium constant, in other words, the bonding strength of the anion to protein is iodide > bromide > chloride.     

Important role of the 3-mercaptopropionamide moiety in glutathione: promoting effect on decomposition of the adduct of glutathione with the oxoammonium ion of TEMPO

Cyclic voltammetry of TEMPO in aqueous 0.1 M NaOH in the presence of glutathione (GSH) or cysteine (Cys) indicated the following points: (i) Both of the thiols rapidly formed adducts 3 with oxoammonium ion 1 anodically generated from TEMPO. (ii) 3 generated from GSH entered a succeeding reaction that generated N-oxide anion 2- (the reduced TEMPO). (iii) 3 produced from Cys remained intact over the time scale of voltammetry. A structural feature of GSH was considered to contribute to the observed behavior of this tripeptide. Possible structural features were evaluated by screening various thiols on the basis of whether they provided GSH-like voltammetric results. The 3-mercaptopropionamide group with an amide hydrogen in GSH was determined to be responsible for the observed difference between GSH and Cys. The likely function is to transform 3 from GSH into a 5-imino-1,2-oxathiolane intermediate, thereby releasing 2-. Product analysis for reactions of model thiols representing GSH and Cys with 1 provided support for this argument and suggested that the reaction of GSH or Cys with 1 would produce the corresponding disulfides, regardless of whether a five-membered ring intermediate was formed. The proposed function of the 3-mercaptopropionamide moiety of GSH may provide useful insight for the molecular design of exogenous thiol compounds as novel drugs for the treatment of GSH-depletion-related disorders.     

Inductively-coupled plasma/atomic emission spectrometry of sulfur with a vacuum scanning spectrometer and its application to the analysis of coal liquefaction catalysts

Inductively-coupled plasma/atomic emission spectrometry with a high-resolution vacuum scanning monochromator is described for the determination of sulfur at 180.734 nm. The behavior of the signal-to-background ratio is investigated as functions of RF power, argon gas flow rate and observation height above the load coil. Under the operating conditions selected, the detection limit is 3 μg l^?1. The Se I 196.090-nm line is chosen as internal standard, because the S/Se line pair exhibited the least change with carrier gas flow rate and acid concentration of solution. Sulfur in NiMo and CoMo/ Al₂O₃ catalysts used for coal liquefaction is determined as S(II) and S(VI) species. The total amount of the species agreed well with the sulfur value obtained by the conventinal combustion method.     

Synthesis and photoinduced memory effect of poly[2-N-carbazolylethyl acrylate-co-2-(3,5-dinitrobenzoyloxy) ethyl methacrylate]

Copolymers containing an intramolecular electron donor-acceptor (EDA) complex were synthesized by free radical copolymerization of 2-N-carbazolylethyl acrylate and 2-(3,5-dinitrobenzoyloxy)ethyl methacrylate. Glass transition temperatures show a positive deviation from the weight-average values of copolymers, indicating the presence of the specific EDA interaction in copolymers in the solid state. Photoinduced “memory effect,” which is defined as the percentage of the difference of the surface potential given by corona charging before and after irradiation of light on polymer films, was 30% for the copolymer with 5 mol% of acceptor content. Memory effect increased to 70% for a 8 μm film by doping with 2 wt% of trichloroacetic acid (TCAA), and leveled off at 5 wt% of TCAA content. Memory effect was also enhanced by increasing the thickness of polymer films and irradiation time. The largest value of memory effect (85%) was obtained from the film of the copolymer with 5 mol% acceptor content doped with 1 wt% TCAA and with thickness larger than 14 μm.     

Analytical approach to the discoloration of edible laver "nori" in the Ariake Sea.

To understand the cause of discoloration of the sea laver "nori," which is found in the Ariake Sea, the concentrations of pigments and elements in the normal and discolored laver samples were determined. In the discolored samples, a decrease in all of the pigments, chlorophyll a and carotenoids, and proteinous pigments, phycobiliproteins, was clearly observed. This was accompanied by a decrease in the content of Fe, Zn, Mn, Cu, and P. Good correlations between these elements and chlorophyll a, as well as between these elements and phycobiliproteins, were confirmed, indicating that, in addition to the deficiency of nitrogen and phosphorus, the deficiency of trace elements (Fe, Zn, Mn, and Cu), which are specifically required for photosynthesis, could be a reason for the discoloration of nori. The cause of elemental deficiency is also discussed.     

A practical asymmetric synthesis of trans-4,5-benzhydrindan-1-ones as a precursor of A-nor B-aromatic steroidal compounds

The enantio-controlled synthesis of trans-4,5-benzhydrindan-1-ones was achieved by means of a stereoselective [4+2] cycloaddition of o-quinodimethanes generated by a thermal cleavage of benzocyclobutene derivatives as a key step. The chiral substrates of the thermal reaction were synthesized by a diastereoselective Grignard addition to the chiral O-isopropylideneglyceroketones connected to a benzocyclobutene ring, which were simply prepared from D-mannitol as a chiral source. This approach can provide a new efficient access to A-nor B-aromatic steroidal compounds.     

Importance of the isopropylidene terminal of geranylgeranyl group for the formation of tetraether lipid in methanogenic archaea

Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the CC bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this CC bond formation.     

Copolymerization of optically active N-bornylmaleimide with vinyl monomers

Optically active N-bornylmaleimide (NBMI) was copolymerized with styrene, methyl methacrylate, and vinylidene chloride with a free-radical catalyst to obtain optically active copolymers. The monomer reactivity ratios for the radical copolymerization of NBMI (M₂) with styrene, methyl methacrylate, and vinylidene chloride were: ST-NBMI, r₁ = 0.13, r₂ = 0.05; MMA-NBMI, r₁ = 2.02, r₂ = 0.16; VCl₂-NBMI, r₁ = 1.15, r₂ = 0.47. The Q-e values for NBMI were Q₂ = 0.48 and e₂ = +1.47. The specific rotation and optical rotatory dispersion of these copolymers were measured. The correlation between the specific rotation and composition of these copolymers was not linear. The value of λ_c for each copolymer was independent of the copolymer composition and the comonomer, being 260 mμ for the St-NBMI system, 262 mμ for the MMA-system, and 260 mμ for the VCl₂-NBMI system. The effects of solvents and temperature on the specific rotation of these copolymers were investigated.     

Interactions between temperature-sensitive hydrogel microspheres and granulocytes

Poly(N-isopropylacrylamide) (PNIPAM) has a low critical solution temperature (LCST) at 32°C in water and the hydrophilicity changes through the LCST. The microspheres whose surface was composed of PNIPAM exhibited phase transition behavior around 32°C. Therefore, the interactions between PNIPAM micropheres and granulocytes depended on the temperature. That is, the oxygen consumption and active oxygen production by cells in contact with PNIPAM-containing microspheres and adhesion of the microspheres to the cell surface were more enhanced above the LCST of PNIPAM than below it, whereas no significant temperature dependence of cell–microspheres interaction was observed in nonthermosensitive microsphere systems. It was suggested that the function of cells could be controlled with temperature using the temperature-sensitive microspheres.