Changeable reactivity of ketyl radicals derived from 2-bromomethyl-2-(3-butenyl)benzocyclic-1-alkanones depending on electron transfer conditions employed

Photoinduced electron transfer reaction of 2-bromomethyl-2-(3-butenyl)benzocyclic-1-alkanones with amines afforded 5-exo radical cyclization products while electron transfer reaction with samarium diiodide produced cyclopropanols.     

Euler-lagrange correspondence of cellular automaton for traffic-flow models

We propose a Euler-Lagrange transformation for cellular automata (CA) by developing new explicit transformation formulas. This transformation is done in the fully discrete level of variables, and corresponds to the well-known continuous version of it which appears in continuous mechanics such as fluid dynamics and plasma physics. Applying this method to the traffic problem, we have obtained the Lagrange representation of a traffic model, and also succeeded in clarifying the relation between different types of traffic models. It is shown that the Burgers CA, which is a corresponding CA of the continuous Burgers equation, plays a central role in considering this relation.     

Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide

Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso‐phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent‐free conditions. The meta‐substituted catalysts exhibited high catalytic performance, whereas the para‐ and ortho‐substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta‐substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240 000 at 120 °C, turnover frequency (TOF)=31 500 h^?1 at 170 °C) at an initial CO₂ pressure of 1.7 MPa; catalyzed the reaction even at atmospheric CO₂ pressure (balloon) at ambient temperature (20 °C); and was applicable to a broad range of substrates, including terminal and internal epoxides.     

Synthesis and Application of a Bidentate Ligand Based on Decafluoro‐3‐phenyl‐3‐pentanol: Steric Effect of Pentafluoroethyl Groups on the Stereomutation of O‐Equatorial C‐Apical Spirophosphoranes

1,1,1,2,2,4,4,5,5,5‐Decafluoro‐3‐phenyl‐3‐pentanol was prepared by a Cannizzaro‐type disproportionation reaction, and the dimetallated compound was used as a bidentate ligand, which is bulkier than the Martin ligand (1,1,1,3,3,3‐hexafluoro‐2‐phenyl‐2‐propanol). A P? H spirophosphorane was synthesized by utilizing the new bidentate ligand, and the structure of the product was essentially the same as that of the P? H phosphorane with Martin ligands. Phosphoranes that exhibit reversed apicophilicity (O‐equatorial) were also synthesized and could be converted into the corresponding stable stereoisomers (O‐apical). The crystal structures of O‐equatorial phosphoranes and the O‐apical isomers were slightly affected by the steric repulsion of pentafluoroethyl groups. Kinetic measurements revealed that the stereomutation of O‐equatorial methylphosphorane to the O‐apical isomer was slowed. The activation enthalpy for the stereomutation of the former to the latter was higher than that of the phosphorane with Martin ligands by 5.1 kcal mol^?1.     

Dimeric Tetrathiafulvalene Linked to pseudo‐ortho‐[2.2]Paracyclophane: Chiral Electrochromic Properties and Use as a Chiral Dopant

A dimeric tetrathiafulvalene installed into a chiral pseudo‐ortho‐[2.2]paracyclophane framework was synthesized as a novel chiral electrochromic material. This compound exhibited pronounced chiroptical properties in the UV‐Vis‐NIR range depending on its redox states without racemization. Each enantiomer was examined as a chiral dopant for nematic liquid crystals (LCs), and the induced helicity of the LC solvent was in accord with that of the tetrathiafulvalene compound.     

First isolation and kinetic study of hypervalent 10-As-5 organoarsenic compounds with a C-apical, O-equatorial configuration

Hypervalent organoarsenic compounds violating the apicophilicity concept were isolated for the first time, and the energy of isomerization of these arsoranes to the more stable stereoisomers appeared to be lower than that of the phosphorus analogues based on the kinetic studies.     

Separation of proteins using supramolecular gel electrophoresis

An amphiphilic low-molecular-weight hydrogelator 1 was synthesized. A tris-glycine-SDS solution gel of 1 was applied for electrophoresis to separate proteins. Centrifugation of a mixture of protein and a hydrogel of 1 enabled the recovery of protein. Various combinations of proteins were applied for supramolecular gel electrophoresis (SUGE), and remarkably poor mobility for small proteins (<45 kDa) was found.     

Anisotropic siloxane-based monolith prepared in confined spaces

When bicontinuous gels are prepared via sol-gel method in a 2-dimensionally (2D) confined space, the gel skeletons in the vicinity of interface of a mold are elongated perpendicular to the interface. This phenomenon was attributed to the dynamic wetting of polymerizing siloxane phase onto the interface of the mold under gravity. In this paper, we report the successful preparation of monolithic columns with an oriented pillar structure in a variety of 2D confined spaces. Starting from a solution, which consists of methyltrimethoxysilane (MTMS), the macroporous structure is prepared in situ by a completely spontaneous process. In the oriented pillar structure, bicontinuous siloxane skeletons deformed or disappeared and most pillars are oriented along the direction of gravity. Gel morphologies with the pillar structure were examined by scanning electron microscopy (SEM) and laser scanning confocal microscopy (LSCM). Geometrical information on gel morphologies was numerically derived from the obtained 3D LSCM images.