Regiocontrol of the Bulk Polymerization of Lysine Ethyl Ester by the Selection of Suitable Immobilized Enzyme Catalysts.

The development of a green and facile method for the controlled synthesis of functional polypeptides is desired for sustainable material applications. In this study, the regioselective synthesis of poly(l-lysine) (polyLys) via enzyme-catalyzed aminolysis was achieved by bulk polymerization of l-lysine ethyl ester (Lys-OEt) using immobilized Candida antarctica lipase Novozym 435 (IM-lipase) or trypsin (IM-trypsin). Structural characterization of the obtained polyLys revealed that IM-lipase resulted solely in ε-linked amide bond formation, whereas IM-trypsin predominantly provided α-linked polyLys. Optimization of the conditions for the bulk polymerization using immobilized enzymes resulted in high monomer conversion and a high degree of polymerization, with excellent regioselectivity. Molecular docking simulations revealed different binding conformations of Lys-OEt to the catalytic pockets of lipase and trypsin, which putatively resulted in different amino moieties being used for amide bond formation. The immobilized enzymes were recovered and recycled for bulk polymerization, and the initial activity was maintained in the case of IM-trypsin. The obtained α- and ε-linked polyLys products exhibited different degradability against proteolysis, demonstrating the possibility of versatile applications as sustainable materials. This enzymatic regioregular control enabled the synthesis of well-defined polypeptide-based materials with a diverging structural variety.

Unconventional Polarization Response in Titanite-Type Oxides due to Hashed Antiferroelectric Domains.

Domains in a crystal, which have crystallographic uniformity and are geometrically segmented, typically arise from various phase transitions. The physical properties within individual domains are inherently the same as those in the homogeneous bulk. As a result, sufficiently large domains have little influence on the bulk properties. However, as the domains decrease in size to the nanoscale, for instance, due to multiple phase instabilities or spatial inhomogeneities, then the materials often acquire exceptional functionalities that are unattainable without these domains. This effect is exemplified by the ultrahigh dielectric and piezoelectric responses observed in ferroelectric oxides with nanoscale polar domains as well as in ferroelectric relaxors with polar nanoclusters. Here, we demonstrate that hashed nanoscale domains in an antiferroelectric material are also capable of boosting dielectric permittivity in an unconventional way. This discovery has been made in an antiferroelectric titanite-type oxide, CaTi(Si1-xGex)O5, in which the permittivity significantly increases when the antiferroelectric order becomes short-range. Our transmission electron microscopy observations have clarified that polar regions simultaneously appear around antiphase boundaries in the antiferroelectric phase of CaTi(Si1-xGex)O5. As the concentration of the antiphase boundary increases, the polar regions become denser and play a crucial role in boosting the permittivity. At the composition of x = 0.5, the value of the permittivity finally reaches double that in the bulk and shows excellent linearity, at least until an electric field of 500 kV/cm is applied. The present findings highlight the promise of domain engineering for boosting the permittivity in antiferroelectrics as a way to develop materials with excellent dielectric properties.

Phylogeographic History of Endangered Hokuriku Salamander, Hynobius takedai (Amphibia: Caudata).

Knowledge of the phylogeographic history of organisms is valuable for understanding their evolutionary processes. To the best of our knowledge, the phylogeographic structure of Hokuriku salamander, Hynobius takedai, an endangered species, remains unclear. This study aimed to elucidate the phylogeographic history of H. takedai, which is expected to be strongly influenced by paleogeographic events. Phylogenetic analysis based on partial sequences of the mitochondrial DNA cytochrome b gene confirmed the genetic independence of H. takedai, and the divergence time with closely related species was estimated to be from the Late Pliocene to the Early Pleistocene. In the phylogenetic tree, two clades were identified within H. takedai, and their haplotypes were found in samples collected from the west and east of the distribution range. These intraspecific divergences were strongly influenced by geohistorical subdivisions of the current major distribution areas in the Middle Pleistocene. One clade was further subdivided and its formation may have been influenced by sea level changes in the Late Pleistocene.

Direct Catalytic Enantioselective Conjugate Addition of α-Substituted Benzyl Nitriles to Alkyl Acrylates.

The first enantioselective copper-catalyzed conjugate addition of α-substituted benzyl nitriles to alkyl acrylates is described. This protocol allows the direct and 100% atom-economic generation of a nitrile-containing quaternary stereogenic center in a highly enantioselective manner. The practical application of our methodology was demonstrated through the concise formal synthesis of (-)-aphanorphine.

Degradation of Graphene in High- and Low-Humidity Air, and Vacuum Conditions at 300-500 K.

Graphene is a fundamental unit of carbon materials and, thus, primary sp2-bonded carbon material. Graphene is, however, easily broken macroscopically despite high mechanical strength, although its natural degradation has rarely been considered. In this work, we evaluate the natural degradation of two-layer graphene in vacuo, in low-humidity air, and in high-humidity air at 300, 400, 450, and 500 K. Over 1000 days of degradation at 300 K, the graphene structure was highly maintained in vacuo, whereas the layer number of graphene tended to decrease in high- and low-humidity air. Water was slightly reacted/chemisorbed on graphene to form surface oxygen groups at 300 K. At 450 and 500 K, graphene was moderately volatilized in vacuo and was obviously oxidized in high- and low-humidity air. Surprisingly, the oxidation of graphene was more suppressed in the high-humidity air than in the low-humidity air, indicating that water worked as an anti-oxidizer of graphene by preventing the chemisorption of oxygen on the graphene surface.