A stereocontrolled synthesis of C-4′ alkylated pyrimidine C-nucleosides

A general, stereocontrolled synthesis of pyrimidine $\text{C}$-nucleosides possessing an alkyl group at the C-1′ or C-4′ position is outlined.     

Temperature dependence of the mixed-valence state of57Fe-atoms produced in57Co-Labelled oxo-centered trinuclear iron acetate complexes

Emission Mössbauer spectra of mixedvalence trinuclear complexes,⁵⁷Co-labelled [CoFe₂O(CH₃CO₂)₆(H₂O)₃] and [CoFe₂O(CH₃CO₂)₆ (py)₃]py were compared with that of [CoCr₂O(CH₃CO₂)₆ (py)₃]py. It was found that the⁵⁷Fe atoms produced in⁵⁷Co-labelled [CoFe₂O(CH₃CO₂)₆(H₂O)₃] and [CoFe₂O(CH₃CO₂)₆ (py)₃]py showed a temperature-dependent mixed-valence state as observed in the absorption Mössbauer spectra of [Fe₃O(CH₃CO₂)₆ (H₂O)₃] and [Fe₃O(CH₃CO₂)₆ (py)₃]py, respectively, while⁵⁷Co-labelled [CoCr₂O(CH₃CO₂)₆ (py)₃]py showed a temperature-independent divalent iron/II/ state. The results indicate that the decayed atoms keep their position at the sites of original⁵⁷Co atoms and that the valence electrons are transferred through the intramolcular bondings.     

High-performance potassium poly(heptazine imide) films for photoelectrochemical water splitting

Photoelectrochemical (PEC) water splitting is an appealing approach by which to convert solar energy into hydrogen fuel. Polymeric semiconductors have recently attracted intense interest of many scientists for PEC water splitting. The crystallinity of polymer films is regarded as the main factor that determines the conversion efficiency. Herein, potassium poly(heptazine) imide (K-PHI) films with improved crystallinity were in situ prepared on a conductive substrate as a photoanode for solar-driven water splitting. A remarkable photocurrent density of ca. 0.80 mA cm⁻² was achieved under air mass 1.5 global illumination without the use of any sacrificial agent, a performance that is ca. 20 times higher than that of the photoanode in an amorphous state, and higher than those of other related polymeric photoanodes. The boosted performance can be attributed to improved charge transfer, which has been investigated using steady state and operando approaches. This work elucidates the pivotal importance of the crystallinity of conjugated polymer semiconductors for PEC water splitting and other advanced photocatalytic applications.

Potassium poly(heptazine imide) photoanode is synthesized, and owing to the improved crystallinity, it has presented a remarkable performance for solar-driven water splitting.     

In-situ HVEM Observations of Dislocation Processes during High Temperature Deformation of Silicon Crystals

The characteristics in the plastic deformation of silicon crystals are first reviewed. Such characteristics have been interpreted quantitatively on the basis of some models on the velocity and the multiplication of dislocations during deformation. The results of the in-situ observations of silicon crystals deformed at elevated temperatures in a HVEM are presented. The slowness and the smoothness in the dislocation motion, the dynamic pile-up as a general mode of the collective motion of dislocations, the formation processes of multiplication centers of dislocations observed during the deformation all support the validity of the models adopted. Dislocation dipoles and Lomer-Cottrell sessiles are observed not to act as strong obstacles which play important roles in the work hardening of the crystals.     

An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni₆(NDI-Hpz)₆(dma)₁₂(NO₃)₆]·5DMA·nH₂O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H₂O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2–2.1) × 10⁻⁴ S cm⁻¹ (pressed pellet), which is superior to that of most NDI-based conductors including metal–organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.

Intrinsically electron-conductive metallocycle was synthesized. π-Radicals play a key role in constructing π-stacked columns among molecular hexagons and achieving high electrical conductivity over 10⁻⁴ S cm⁻¹ in polycrystalline pellet.     

Controlled assembly of silica microspheres in spherically confined polymer particles by using self-organized precipitation (SORP) method

Assembly of submicron-sized microspheres has received much attention due to its high potential for wide variety of applications. We have developed a preparation method of polymer particles by simple mixing of a poor solvent into the polymer solution followed by evaporation of a good solvent. By using this technique, silica nanoparticles and polymer composite particles were prepared. Preparation of three-dimensional assemblies of silica particles in polymer particles and composite Janus particles are shown.     

Temperature dependence of the linewidth of the first-order Raman spectra for MnF2 crystal

The first-order Raman spectra ofE _gandA _1g modes in MnF₂ crystal were measured at temperatures from 4.2 to 563 K, and the values of the linewidths obtained. The temperature dependence of the linewidths was analyzed by the phonon dispersion curves based on the rigid ion model, and the result showed that it was caused approximately by the cubic anharmonic term in crystal potential energy.     

Output and picosecond amplification characteristics of an efficient and high-power discharge excimer laser

Improvements in output pulse energy and efficiency of a conventional capacitor-transfer-type discharge excimer laser with automatic preionization have been achieved by extending the discharge volume and resulting moderate pumping of the active medium. The discharge laser produces a pulse energy of more than 1 J for XeCl, KrF, and ArF lasers in square beams of about 2×2 cm², and the maximum overall efficiency observed is 2.9% for XeCl, 3.2% for KrF and 1.8% for ArF. The laser device has been involved in a picosecond ( 32 ps) XeCl laser amplification system, and was operated as an amplifier at a repetitive frequency of 10 Hz. Saturation fluence for XeCl laser was measured to be 1.4 mJ/cm², and the picosecond pulse energy of 40 mJ was extracted from the amplifier.On leave from Ebara Corp., 6-6-7, Ginza, Chuo-ku, Tokyo 104, JapanOn leave from Mitsubishi Heavy Industries, LTD., 4-6-22, Kan-on shinmachi, Nishi-ku, Hiroshima 733, Japan