Asymmetric reduction of 2-substituted 2-butenolides with reductase from Marchantia polymorpha

A p68 reductase participating in the asymmetric reduction of the C–C double bond of 2-substituted 2-butenolides was isolated from Marchantia polymorpha. The enzyme reduced 2-substituted 2-butenolides to give (R)-butanolides, and the reduction of citraconic anhydride afforded (R)-methylsuccinic anhydride.     

Polyesters containing ring units in main chains. I. Preparation and stereochemistry of monomers and polyesters

Cycloalkanone (C₅–C₈, C₁₂, and C₁₅) or cycloalkane (C₅ and C₆) ring-containing monomeric diesters and the polyesters derived from them were prepared, and their configurations were studied by ¹³C-NMR spectroscopy. Absolute configurations were determined for ring sizes 5, 6, and 7. Configurational change during reduction of a ketonic group of monomeric diesters with ring sizes 5 and 6 was discussed in terms of the steric effect of ring substituents on the ketonic group. In the polycondensation reaction epimerization of the ring units was observed in 5-, 6-, and 7-membered cycloalkanones and not in others, which is explained by steric hindrance by the ring substituents against attack of tetrabutyl titanate catalyst on the ketonic group.     

Further evidence for the intramolecular charge-transfer interaction between tropylium ion and remote benzene rings in 9,10-dihydro-9,10-(1,2-tropylio)anthracene tetrafluoroborate and its methyl derivatives

A series of 9,10-dihydro-9,10-(1,2-tropylio)anthracene tetrafluoroborates

has been prepared. The intramolecular charge-transfer interactions in

were confirmed by their UV spectra and pK_R+ values. As a model compound 1,2,3,4-tetrahydro-1,4-(1,2-tropylio)naphthalene tetrafluoroborate ($\text{5}$)_was also examined.     

Formation of tetrahydrocurcumin by reduction of curcumin with cultured plant cells of Marchantia polymorpha

Cultured plant cells of Marchantia polymorpha, Nicotiana tabacum, Phytolacca americana, Catharanthus roseus, and Gossypium hirsutum were examined for their ability to reduce curcumin. Only M. polymorpha cells converted curcumin into tetrahydrocurcumin in 90% yield in one day. Time-course experiment revealed a two-step formation of tetrahydrocurcumin via dihydrocurcumin.     

Polyesters containing ring units in the main chain. II. Effects of size and mobility of rings on molecular relaxations

Molecular relaxations of polyesters containing C₅–C₁₅ rings in the main chain have been studied by DSC, dielectric dispersion, and NMR. Results are discussed in relation to the size and mobility of the rings. The T_g or α-relaxation peak moves to higher temperature with an increase in the ring size from C₅ to C₁₂, but the effect is accompanied by an even–odd alternation with ring size. The β relaxations in dielectric dispersion reflect local-mode motion of ester groups and are affected by steric interactions with the rings. Motions of the ring methylenes of C₁₂ and C₁₅ ring units are detected below T_g by broad-line NMR.     

Chemo-enzymatic synthesis of ester-linked docetaxel-monosaccharide conjugates as water-soluble prodrugs

Three new docetaxel prodrugs, i.e., 7-propionyldocetaxel 3'-O-β-D-glycopyranosides, which contain ester-linked monosaccharides, were synthesized by a chemo-enzymatic procedure involving enzymatic transglycosylations with lactase, β-galactosidase, or β-xylosidase. The water-solubility of 7-propionyldocetaxel 3'-O-β-D-glucopyranoside was 52-fold higher than that of docetaxel. 7-Propionyldocetaxel 3'-O-β-D-glucopyranoside and 7-propionyldocetaxel 3'-O-β-D-xylopyranoside were effectively hydrolyzed by the relevant enzyme(s) of human cancer cells to release docetaxel, whereas 7-propionyldocetaxel 3'-O-β-D-galactopyranoside was relatively resistant under similar conditions. 7-Propionyldocetaxel 3'-O-β-D-glucopyranoside and 7-propionyldocetaxel 3'-O-β-D-xylopyranoside showed in vitro cytotoxic activity against human cancer cells, whereas 7-propionyldocetaxel 3'-O-β-D-galactopyranoside exerted low cytotoxicity.     

Glycosylation of vanillin and 8-nordihydrocapsaicin by cultured Eucalyptus perriniana cells

Glycosylation of vanilloids such as vanillin and 8-nordihydrocapsaicin by cultured plant cells of Eucalyptus perriniana was studied. Vanillin was converted into vanillin 4-O-β-D-glucopyranoside, vanillyl alcohol, and 4-O-β-D-glucopyranosylvanillyl alcohol by E. perriniana cells. Incubation of cultured E. perriniana cells with 8-nordihydrocapsaicin gave 8-nordihydrocapsaicin 4-O-β-D-glucopyranoside and 8-nordihydrocapsaicin 4-O-β-D-gentiobioside.     

Self-discharge characteristics of an electric double-layer capacitor with polymer hydrogel electrolyte

An electric double-layer capacitor (EDLC) was assembled with the polymer hydrogel electrolyte prepared from cross-linked potassium poly(acrylate) (PAAK) and KOH aqueous solution, and the self-discharge characteristics were investigated. The EDLC cell with the polymer hydrogel electrolyte showed lower voltage decay on open circuit than that with a KOH aqueous solution. Moreover, it was found that the leakage current of the EDLC cell was markedly suppressed by using the polymer hydrogel electrolyte. The suppression was enhanced with increasing PAAK content in the electrolyte. These results strongly suggest that the PAAK plays an important role in the suppression of self-discharge.