Oxidative trans to cis Isomerization of Olefins in Polyketide Biosynthesis

Geometric isomerization can expand the scope of biological activities of natural products. The observed chemical diversity among the pseurotin‐type fungal secondary metabolites is in part generated by a trans to cis isomerization of an olefin. In vitro characterizations of pseurotin biosynthetic enzymes revealed that the glutathione S‐transferase PsoE requires participation of the bifunctional C‐methyltransferase/epoxidase PsoF to complete the trans to cis isomerization of the pathway intermediate presynerazol. The crystal structure of the PsoE/glutathione/presynerazol complex indicated stereospecific glutathione–presynerazol conjugate formation is the principal function of PsoE. Moreover, PsoF was identified to have an additional, unexpected oxidative isomerase activity, thus making it a trifunctional enzyme which is key to the complexity generation in pseurotin biosynthesis. Through the study, we identified a novel mechanism of accomplishing a seemingly simple trans to cis isomerization reaction.     

Associative desorption of adsorbed oxygen promoted by translational energy of incident O2 molecules

Effects of the translational energy of incident oxygen molecules on surface processes from dissociative adsorption to subsequent associative desorption on Pt(1 1 1) have been investigated by means of supersonic molecular beam scattering. The reaction rate of associative desorption increases with the incident translational energy. The enhanced associative desorption can be attributed to nonthermal diffusion of dissociated oxygen, promoted by the translational energy of incoming molecules.     

Laser-induced pinpoint hydrogen evolution from benzene and water using metal free single-walled carbon nanotubes with high quantum yields

Metal-free photocatalytic hydrogen evolution occurred efficiently in benzene containing single-walled carbon nanotubes under laser irradiation at 532 nm with an extremely high turnover number of 2 000 000 and a high quantum yield of 130%. The rate of hydrogen evolution increased with increasing laser intensity to exhibit a fourth power dependence, suggesting that hydrogen was evolved via four-photon processes in which the coupling of two radical anions derived from benzene is the rate-determining step and the benzene radical anion is produced by electron transfer from benzene to the doubly excited state of single-walled carbon nanotubes, which requires two photons. Polymerisation of benzene was induced by the photogenerated C₆H₆˙^–, accompanied by hydrogen evolution, resulting in a leverage effect to increase the quantum yield of hydrogen evolution to well over the 25% expected for the four-photon process. Laser-induced hydrogen evolution also occurred in water containing single-walled carbon nanotubes. In contrast to the case of benzene, water was not oxidized but hydrogen evolution from water was accompanied by the multi-oxidation of single-walled carbon nanotubes. The yield of hydrogen based on one mole of single-walled carbon nanotubes with 1.4 nm diameter and 1–5 mm length was determined to be 2 700 000%, when oxidations of single-walled carbon nanotubes occurred to produce the polyhydroxylated product.     

Blending to Make Nonhealable Polymers Healable: Nanophase Separation Observed by CP/MAS 13C NMR Analysis

Can commodity polymers are made to be healable just by blending with self-healable polymers? Here we report the first study on the fundamental aspect of this practically challenging issue. Poly(ether thiourea) (PTUEG₃; T_g=27 °C) reported in 2018 is extraordinary in that it is mechanically robust but can self-heal even at 12 °C. In contrast, poly(octamethylene thiourea) (PTUC₈; T_g=50 °C), an analogue of PTUEG₃, cannot heal below 92 °C. We found that their polymer blend self-healed in a temperature range above 32 °C even when its PTUEG₃ content was only 20 mol %. Unlike PTUEG₃ alone, this polymer blend, upon exposure to high humidity, barely plasticized, keeping its excellent mechanical properties due to the non-hygroscopic nature of the PTUC₈ component. CP/MAS ¹³C NMR analysis revealed that the polymer blend was nanophase-separated, which possibly accounts for why such a small amount of PTUEG₃ provided the polymer blend with humidity-tolerant self-healable properties.     

Synthesis of functionalized pentacenes from isobenzofurans derived from C-H bond activation

The synthesis of unsymmetric functionalized pentacenes from 1,4-anthraquinones and functionalized isobenzofurans, which were prepared by transformation via C-H bond activation, was successfully accomplished. Examples of the synthesis of pentacenes with functional groups at the 5-position are still rare. These obtained functionalized pentacenes are highly soluble in hexane, toluene, and THF.     

Enantioseparation of 3-Hydroxycarboxylic Acids via Diastereomeric Salt Formation by 2-Amino-1,2-diphenylethanol (ADPE) and Cinchonidine

Enantioseparation of 3-hydroxycarboxylic acids via diastereomeric salt formation was demonstrated using 2-amino-1,2-diphenylethanol (ADPE) and cinchonidine as the resolving agents. Racemic 3-hydroxy-4-phenylbutanoic acid (rac-1), 3-hydroxy-4-(4-chlorophenyl)butanoic acid (rac-2), and 3-hydroxy-5-phenylpentanoic acid (rac-3) were efficiently resolved using these resolving agents. Moreover, the successive crystallization of the less-soluble diastereomeric salt of 1 and cinchonidine using EtOH yielded pure (R)-1 · cinchonidine salt in a high yield. The crystal structures of less-soluble diastereomeric salts were elucidated and it was revealed that hydrogen bonding and CH/π interactions play an important role in reinforcing the structure of the less-soluble diastereomeric salts.     

tert‐Butyl Iodide Mediated Reductive Fischer Indolization of Conjugated Hydrazones

A novel reductive Fischer indolization of readily available N‐aryl conjugated hydrazones with tert‐butyl iodide has been developed. In this reaction, tert‐butyl iodide is used as anhydrous HI source, and the generated HI acts as a Brønsted acid and a reducing agent. This operationally simple method allows access to various indole derivatives. Furthermore, the procedure can be applied to the synthesis of biologically active compounds.     

Adsorption behavior of natural anthocyanin dye on mesoporous silica

Because of its non-toxicity, naturally occurring anthocyanin is potentially suitable as a colorant for foods and cosmetics. To the wider use of the anthocyanin, the immobilization on the inorganic host for an easy handling as well as the improvement of the stability is required. This study is focused on the adsorption of significant amount of the natural anthocyanin dye onto mesoporous silica, and on the stability enhancement of the anthocyanin by the complexation. The anthocyanin has successfully been adsorbed on the HMS type mesoporous silica containing small amount of aluminum. The amount of the adsorbed anthocyanin has been increased by modifying the pore wall with n-propyl group to make the silica surface hydrophobic. The light fastness of the adsorbed anthocyanin has been improved by making the composite with the HMS samples containing aluminum, although the degree of the improvement is not so large. It has been proposed that incorporation of the anthocyanin molecule deep inside the mesopore is required for the further enhancement of the stability.