Energy Dissipation Processes of singlet‐excited 1‐Hydroxyfluorenone and its Hydrogen‐bonded Complex with N‐methylimidazole¶

Effects of solvent, pH and hydrogen bonding with N‐methylimidazole (MIm) on the photophysical properties of 1‐hydroxyfluorenone (1HOF) have been studied. Fluorescence lifetime, fluorescence quantum yield and triplet yield measurements demonstrated that intersystem crossing was the dominant process in apolar media and its rate constant significantly diminished with increasing solvent polarity. The acceleration of internal conversion in alcohols paralleled the strength of intermolecular hydrogen bonding. The faster energy dissipation from the singlet‐excited state in cyclohexane was attributed to intramolecular hydrogen bonding. The pK_a of 1HOF decreased from 10.06 to 5.0 on light absorption, and H₃O⁺ quenched the singletexcited molecules in a practically diffusion‐controlled reaction. On addition of MIm in toluene, dual fluorescence was observed, which was attributed to reversible formation of excited hydrogen‐bonded ion pair. Rate constants for the various deactivation pathways were derived from the combined analysis of the steady‐state and the time‐resolved fluorescence results.     

Effects of Roxadustat on Erythropoietin Production in the Rat Body

Anemia is a major complication of chronic renal failure. To treat this anemia, prolylhydroxylase domain enzyme (PHD) inhibitors as well as erythropoiesis-stimulating agents (ESAs) have been used. Although PHD inhibitors rapidly stimulate erythropoietin (Epo) production, the precise sites of Epo production following the administration of these drugs have not been identified. We developed a novel method for the detection of the Epo protein that employs deglycosylation-coupled Western blotting. With protein deglycosylation, tissue Epo contents can be quantified over an extremely wide range. Using this method, we examined the effects of the PHD inhibitor, Roxadustat (ROX), and severe hypoxia on Epo production in various tissues in rats. We observed that ROX increased Epo mRNA expression in both the kidneys and liver. However, Epo protein was detected in the kidneys but not in the liver. Epo protein was also detected in the salivary glands, spleen, epididymis and ovaries. However, both PHD inhibitors (ROX) and severe hypoxia increased the Epo protein abundance only in the kidneys. These data show that, while Epo is produced in many tissues, PHD inhibitors as well as severe hypoxia regulate Epo production only in the kidneys.     

Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Comparison of CO2 Reduction Performance with NH3 and H2O between Cu/TiO2 and Pd/TiO2

The aim of this study is to clarify the effect of doped metal type on CO₂ reduction characteristics of TiO₂ with NH₃ and H₂O. Cu and Pd have been selected as dopants for TiO₂. In addition, the impact of molar ratio of CO₂ to reductants NH₃ and H₂O has been investigated. A TiO₂ photocatalyst was prepared by a sol-gel and dip-coating process, and then doped with Cu or Pd fine particles by using the pulse arc plasma gun method. The prepared Cu/TiO₂ film and Pd/TiO₂ film were characterized by SEM, EPMA, TEM, STEM, EDX, EDS and EELS. This study also has investigated the performance of CO₂ reduction under the illumination condition of Xe lamp with or without ultraviolet (UV) light. As a result, it is revealed that the CO₂ reduction performance with Cu/TiO₂ under the illumination condition of Xe lamp with UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:1:1 while that without UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:0.5:0.5. It is revealed that the CO₂ reduction performance of Pd/TiO₂ is the highest for the molar ratio of CO₂/NH₃/H₂O = 1:1:1 no matter the used Xe lamp was with or without UV light. The molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp with UV light was 10.2 μmol/g, while that for Pd/TiO₂ was 5.5 μmol/g. Meanwhile, the molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp without UV light was 2.5 μmol/g, while that for Pd/TiO₂ was 3.5 μmol/g. This study has concluded that Cu/TiO₂ is superior to Pd/TiO₂ from the viewpoint of the molar quantity of CO per unit weight of photocatalyst as well as the quantum efficiency.     

Determination of selenium in human serum by liquid chromatography/electron capture atmospheric pressure chemical ionization mass spectrometry after acid digestion and derivatization using 2,3-diaminonaphthalene

Analysis of selenium in biological samples is very important and numerous analytical methods for the element have been developed. One of the most convenient and widely used methods for routine determination of serum selenium is a fluorometric method using 2,3-diaminonaphthalene (DAN); however, this method lacks specificity. We observed that 4,5-benzopiazselenol (BPS), a selenium derivative of DAN, is ionized with electron capture in an atmospheric pressure chemical ionization (APCI) interface, and subsequently established a method for determining total human serum selenium by means of liquid chromatography/atmospheric pressure chemical ionization mass spectrometry. All pretreatment procedures were carried out in a single test tube to minimize selenium loss. The recovery of organic or inorganic selenium spiked to human serum was 97-103%.The detection limit of BPS was equivalent to 0.2 ng of selenium and the lower quantitative limit of serum selenium was 10 ng mL(-1). The coefficient of variation of standard concentrations in control serum samples was 4.5%. The purity of the observed peak obtained from serum samples was confirmed using the ion cluster technique.     

Total synthesis of leustroducsin B

A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).     

Quenching of bacteriochlorophyll fluorescence in chlorosomes from Chloroflexus aurantiacus by exogenous quinones

The quenching of bacteriochlorophyll (BChl) c fluorescence in chlorosomes isolated from Chloroflexus aurantiacus was examined by the addition of various benzoquinones, naphthoquinones (NQ), and anthraquinones (AQ). Many quinones showed strong quenching in the micromolar or submicromolar range. The number of quinone molecules bound to the chlorosomes was estimated to be as small as one quinone molecule per 50 BChl c molecules. Quinones which exhibit a high quenching effect have sufficient hydrophobicity and one or more hydroxyl groups in the alpha positions of NQ and AQ. Chlorobiumquinone has been suggested to be essential for the endogenous quenching of chlorosome fluorescence in Chlorobium tepidum under oxic conditions. We suggest that the quenching effect of chlorobiumquinone in chlorosomes from Chl. tepidum is related to the 1'-oxo group neighboring the dicarbonyl group.     

Synthesis and structure of 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines

Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substituents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key compound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine, which is a precursor for other azabismocines, has been synthesized by two different procedures; one is based on Akiba’s method using 2-bromobenzylbromide as one of the starting materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12 new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to be highly flexible and the hypervalent Bi-N bond distances vary ranging from 2.568(3) to 2.896(5) Å, depending on the electronic nature of the substituents on the bismuth atom. The Bi-N bond distances have good linear relationship against Hammett’s σ_m constants.     

Synthesis and lyotropic liquid crystal properties of chiral helical polycarbodiimides

Chiral helical polymers have been expected to exhibit optical activity with a significantly large optical rotation power. In this paper polymethylphenylethylcarbodiimides (Poly-PhEMCDI) with helical structure were synthesized by the insertion polymerization of a corresponding chiral monomeric carbodiimide initiated by a copper complex. The circular dichroism spectra and optical rotation power induced by the ordered rigid main chain helical structure of polycarbodiimides, in solution and as cast films, were studied. Polycarbodiimides have a rigid rod helical structure and form lyotropic liquid crystal (LLC) in organic solvents such as dichloromethane (DCM), chloroform and THF. The LLC phase was studied using polarizing optical microscopy and X-ray diffraction. A chiral nematic phase was formed in DCM and chloroform in the concentration range 20–36%. Spherulites were formed in more concentrated solution. The formation of a LLC phase in polycarbodiimides organic solutions makes it possible to align the polymer helical chain to form an ordered film for electro-optical applications.