Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).     

Flavin-catalyzed aerobic oxidation of sulfides in aqueous media

An aerobic, organocatalytic, and aqueous method for the oxidation of sulfides is described. Synthetic flavin, 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate, acts as an efficient catalyst for the oxidation of sulfides in water under an oxygen atmosphere (1 atm) with the assistance of ascorbic acid as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides.     

Yeasts and Lactic Acid Bacteria Mixed-Specie Biofilm Formation is a Promising Cell Immobilization Technology for Ethanol Fermentation

We previously found that some Saccharomyces cerevisiae and Lactobacillus plantarum remarkably formed mixed-specie biofilm in a static co-culture and deduced that this biofilm had potential as immobilized cells. We investigated the application of mixed-specie biofilm formed by S. cerevisiae BY4741 and L. plantarum HM23 for ethanol fermentation in repeated batch cultures. This mixed-specie biofilm was far abundantly formed and far resistant to washing compared with S. cerevisiae single biofilm. Adopting mixed-specie biofilm formed on cellulose beads as immobilized cells, we could produce enough ethanol from 10 or 20 % glucose during ten times repeated batch cultures for a duration of 10 days. Cell numbers of S. cerevisiae and L. plantarum during this period were stable. In mixed-specie biofilm system, though ethanol production was slightly lower compared to S. cerevisiae single-culture system due to by-production of lactate, pH was stably maintained under pH 4 without artificial control suggesting high resistance to contamination. Inoculated model contaminants, Escherichia coli and Bacillus subtilis, were excluded from the system in a short time. From the above results, it was indicated that the mixed-specie biofilm of S. cerevisiae and L. plantarum was a promising immobilized cell for ethanol fermentation for its ethanol productivity and robustness due to high resistance to contamination.     

7,7,8,8‐Tetraaryl‐o‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 ²⁺, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b ²⁺ and 2 c ²⁺, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 ²⁺ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.     

Preparation of Molecule‐Responsive Microsized Hydrogels via Photopolymerization for Smart Microchannel Microvalves

Microdevices designed for practical environmental pollution monitoring need to detect specific pollutants such as dioxins. Bisphenol A (BPA) has been widely used as a monomer for the synthesis of polycarbonate and epoxy resins. However, the recent discovery of its high potential ability to disrupt human endocrine systems has made the development of smart systems and microdevices for its detection and removal necessary. Molecule‐responsive microsized hydrogels with β‐cycrodextrin (β‐CD) as ligands are prepared by photopolymerization using a fluorescence microscope. The molecule‐responsive micro‐hydrogels show ultra‐quick shrinkage in response to target BPA. Furthermore, the flow rate of a microchannel is autonomously regulated by the molecule‐responsive shrinking of their hydrogels as smart microvalves.

     

Prediction of cellulose nanotube models through density functional theory calculations

We report the generation of a nano-scale tubular structure of cellulose molecules (CelNT), through density functional theory (DFT) calculations. When a cellulose III_I (1 0 0) chain sheet model is optimized by DFT calculations, the sheet models spontaneously roll into tubes. The oligomers arrange in a right-handed, four-fold helix with one-quarter chain staggering, oriented with parallel polarity similar to the original crystal structure. Based on a one-quarter chain staggering relationship, six large CelNT models, consisting of 16 cellulose chains with DP = 80, are constructed by combinations of two types of chain polarities and three types of symmetry operations to generate a circular arrangement of molecular chains. All six CelNT models are examined by molecular dynamics (MD) calculations in chloroform. While four CelNT models retain a tubular form throughout MD calculations, the remaining two deform. 3D-RISM theory model is used to estimate the solvation free energies of the four CelNT models. The results suggest that the CelNT model with a chain arrangement of parallel polarity and right-handed helical symmetry forms the most stable tube structure.