Kinetics of Iterative Carbohydrate Transfer to Polysaccharide Catalyzed by Chondroitin Polymerase on a Highly Sensitive Flow‐Type 27 MHz Quartz‐Crystal Microbalance

Using a highly sensitive flow‐type 27 MHz quartz crystal microbalance, we could detect a small mass change during stepwise and alternating one‐sugar transfer of glucuronic acid (GlcA) and N‐acetylgalactosamine (GalNAc) to an acceptor, catalyzed by chondroitin polymerase from Escherichia coli strain K4 (K4CP), and analyze the elongation mechanism of K4CP. K4CP was found to bind strongly to a chondroitin acceptor (K_d=0.97 μM ). Although the binding affinity and the catalytic rate constant for each monomer were considerably different, the apparent catalytic efficiency (k_cat/K_m) was similar (6.3×10⁴ M ^?1 s^?1 for GlcA transfer and 3.4×10⁴ M ^?1 s^?1 for the GalNAc transfer). This is reasonable for the smooth alternating elongation of GlcA and GalNAc on the acceptor. This is the first study to report the determination of kinetic parameters for enzymatic, alternated, sugar elongation.     

Heterocyclic effect for optical properties of naphthoquinone-based pigment: 2-methyl-3-heteroarylthio-1,4-naphthalenedione

Three novel naphthoquinone-based heterocyclic pigments, 2-methyl-3-[(1-methyl-1H-imidazol-2-yl)thio-1,4-naphthalenedione, (4-methyl-4H-1,2,4-triazol-3-yl)thio-1,4-naphthalenedione, and (1-methyl-1H-tetrazol-5-yl)thio]-1,4-naphthalenedione, are synthesized, and their optical properties in both solution and solid states are investigated. Depending on the heteroarylthio ring in the pigment, variation in optical properties is observed, e.g. characteristic colours for each pigment in the solution and solid states. The achiral pigment containing the 1-methyl-1H-tetrazol-5-yl ring exhibits a chiral space group and a CD signal in the solid state.     

Mössbauer study of the fraction of non-bridging oxygens in potassium borate glasses

A Mössbauer study was performed to find the fraction of non-bridging oxygens in potassium borate glasses containing a small amount of iron. The borate glasses with alkali contents of 15, 20, 25, 30 and 40 mol% were irradiated with ⁶⁰Co-γ rays at room temperature in a nitrogen atmosphere. The Mössbauer absorption area for the irradiation-induced Fe²⁺ increased with the total γ-ray dose in the range of 1 × 10⁶ ?2 × 10⁸ R, and became constant after irradiation ranging from 2 × 10⁸ R ? 1 × 10⁹ R. The absorption area for the Fe²⁺ at the saturated region was correlated with the difference in the glass structure, i.e., the fraction of the non-bridging oxygens was estimated from the increased absorption area for the Fe²⁺ as a function of the alkali content of the glasses. The fraction of the non-bridging oxygen increased with the alkali content of the glasses in the alkali region above 20 mol%, and about 14% of the fraction was obtained for an alkali content of 40 mol%.     

Stereospecific photocyclization of α-bisulfenylated keto compounds. Cis-dihydrobenzothiophenes

Irradiation of α-bisulfenylated keto compounds in acetonitrile affords the cis-fused dihydrobenzothiophenes which are dehydrated to benzothiophenes in high yields.