Ab initio MO study on [3 + 2] annulation using beta-phenylthio-acryloylsilanes with alkyl methyl ketone enolates and its through-space/bond interaction analysis

Ab initio through-space/bond interaction analysis was applied to [3 + 2] annulation based on Brook rearrangement using beta-phenylthio-acryloylsilanes with alkyl methyl ketone enolates. An uncertain reaction mechanism, wherein a bulky cyclopentenol with large substituents on the same side of the five-membered ring was obtained as a major product, can be explained by the low activation energy of its reaction pathway. Intramolecular orbital interactions related to the carbanion generated by Brook rearrangement preferentially provide the stabilization of the reaction pathway to the bulky cyclopentenol (major product) compared with that provided to the non-bulky cyclopentenol (minor product). In addition, ab initio molecular orbital calculations suggest the existence of an E/Z conformational inversion after Brook rearrangement. This result accurately explains the loss of the E/Z stereochemical integrity in the starting materials of the experiment.     

Alkali metal and alkali metal hydroxide intercalates of 2s-tantalum disulfide

The alkali metal intercalates of the layered compound 2s-tantalum disulfide were prepared from the respective hexamethylphosphoric triamide solutions of the metals. The c-lattice parameters of the intercalates increased with increase in the crystallographic radii of the metals. All intercalates prepared were superconductors, and the transition temperatures increased as the crystallographic radii of the metals became larger. The intercalates reacted with water to produce hydrogen gas and changed to different intercalates. These had properties similar to those of the corresponding alkali metal hydroxide intercalates prepared from aqueous solutions of the metal hydroxides. The alkali metal hydroxide intercalates, on the other hand, were found to be classified into two groups in terms of the c-lattice parameters; one having c-lattice parameters around 23.8 Å and the other 18 Å. Lithium and sodium hydroxide intercalates belong to the former type, and potassium, rubidium and cesium hydroxide intercalates, including ammonium hydroxide, to the latter. Dried lithium and sodium hydroxide intercalates were also classified in the latter group. In the former case the disulfide was found to intercalate the cations, conserving the ice-like structure of the surrounding water molecules. In the latter, the cations were intercalated in their naked or primary hydrated states, and the interlayer distances were governed by cointercalated hydroxide ions. The observed superconducting transition temperatures were similar for the intercalates with c-lattice parameters around 18 Å irrespective of the particular cation.     

Visible‐Light‐Responsive Photoanodes for Highly Active,Stable Water Oxidation

Solar energy is a natural and effectively permanent resource and so the conversion of solar radiation into chemical or electrical energy is an attractive, although challenging, prospect. Photo‐electrochemical (PEC) water splitting is a key aspect of producing hydrogen from solar power. However, practical water oxidation over photoanodes (in combination with water reduction at a photocathode) in PEC cells is currently difficult to achieve because of the large overpotentials in the reaction kinetics and the inefficient photoactivity of the semiconductors. The development of semiconductors that allow high solar‐to‐hydrogen conversion efficiencies and the utilization of these materials in photoanodes will be a necessary aspect of achieving efficient, stable water oxidation. This Review discusses advances in water oxidation activity over photoanodes of n‐type visible‐light‐responsive (oxy)nitrides and oxides.     

Formation and Isolation of a Four‐Electron‐Reduced Porphyrin Derivative by Reduction of a Stable 20π Isophlorin

The two‐electron reduction of a diprotonated dodecaphenylporphyrin derivative by Na₂S₂O₄ gave a corresponding isophlorin ( Iph ) selectively. Formation of Iph was confirmed by spectroscopic measurements and the isolation of tetramethylated Iph . Further reduction of Iph proceeded to form an unprecedented four‐electron‐reduced porphyrin ( IphH₂ ), which was fully characterized by spectroscopic and X‐ray crystallographic analysis. IphH₂ , with a unique conformation, could be oxidized to reproduce the starting porphyrin, resulting in a proton‐coupled four‐electron reversible redox system.     

Photocatalytic water reduction under visible light on a novel ZnIn2S4 catalyst synthesized by hydrothermal method

A novel ZnIn2S4 catalyst synthesized by hydrothermal method shows high and stable photocatalytic activity for water reduction under visible light illumination.     

On a Mathematical Comparison between Hierarchy and Network with a Classification of Coordination Structures

This paper proposes a mathematical model to compare a network organization with a hierarchical organization. In order to formulate the model, we define a three-dimensional framework of the coordination structure of a network and of other typical coordination structures. In the framework, we can define a network structure by contrasting it with a hierarchy, in terms of the distribution of decision making, which is one of the main features of information processing. Based on this definition, we have developed a mathematical model for evaluating coordination structures. Using this model, we can derive two boundary conditions among the coordination structures with respect to the optimal coordination structure. The boundary conditions help us to understand why an organization changes its coordination structure from a hierarchy to a network and what factors cause this change. They enable us, for example, to find points of structural change where the optimal coordination structure shifts from a hierarchy to a hierarchy with delegation or from a hierarchy with delegation to a network, when the nature of the task changes from routine to non-routine. In conclusion, our framework and model may provide a basis for discussing the processes that occur when coordination structures change between a hierarchy and a network.     

Synthesis and nucleic acid-binding properties of water-soluble porphyrins appending platinum(II) complexes.

We synthesized two water-soluble porphyrins appending platinum(II) complexes [alpha,beta-(4a) and alpha,alpha-(4b) 5,15-bis(2-trans-[PtCl(NH3)2]N-2-aminoethylaminocarbonylphenyl) 2,3,7,8,12,13,17,18-octamethylporphyrin] and studied their reactions with a variety of nucleic acids [disodium adenosine-5'-monophosphate (AMP), disodium guanosine-5'-monophosphate (GMP), disodium thymidine-5'-monophosphate (TMP), disodium cytidine-5'-monophosphate (CMP), synthetic polymer poly(dG)-poly(dC), poly(dA)-poly(dT)] by 1H-NMR, UV-vis and FAB-MS spectroscopies. Based on the denaturation experiments of synthetic nucleic acid polymers, we conclude that the presence of the porphyrins (5.6 microM) does not cause significant changes in the melting temperature of poly(dA)-poly(dT) (28 microM) (deltaT=1 degrees C) and shows reannealing. On the other hand, gradual melting of poly(dG)-poly(dC) (28 microM) occurs at a low temperature (deltaT= -27 degrees C) in the presence of the porphyrins (5.6 microM), and the solutions do not show reannealing phenomena. The results of UV-vis and 1H-NMR experiments revealed that the porphyrins bind to guanine bases and that the porphyrins bind to GMP more strongly than to the other nucleotides. The binding modes between the porphyrins and synthetic nucleic acids are affected more by the coordination of the nucleobase [poly(dG)-poly(dC)] to the Pt(II) in the porphyrins than by Coulomb and hydrophobic interactions.