Solid-phase syntheses of olefin-containing inhibitors for HTLV-1 protease using the Horner-Emmons reaction

[reaction: see text] The solid-phase Horner-Emmons reaction was successfully applied for the convenient syntheses of olefin-containing protease inhibitors. The isomerization during the solid-phase Horner-Emmons reaction can be minimized simply by the use of an appropriate amount of the base. The synthesized olefin peptides, which have an olefin gamma-amino acid at the scissile site, were found to act as effective inhibitors for the HTLV-1 protease for the first time.     

Crystallized state,thickening process,and crystal transformation of single crystal of trans-1,4-polybutadiene

The effect of heat treatment of trans-1,4-polybutadiene single crystals prepared from dilute benzene solution was studied by dilatometry, X-ray diffraction, and dynamic viscoelastic measurement. The crystal transformation temperature of the single crystal is 55.5[ddot]C, 20[ddot]C lower than that of the bulk crystallized sample. After heat treatment of the single crystal above 55.5[ddot]C, their crystal transformation temperature increases to 69.5[ddot]C. At the same time, thickening of the lamellae suddenly occurs and the viscoelastic primary absorption observed in the single crystal mat disappears. It is suggested that this means that the amorphous region attached to the single crystal rapidly crystallized above this temperature, in particular the loose loops attached to the end surface of the crystal are dragged into the crystalline phase to form tight loops as a result of the sliding diffusion of molecules along their axes. This is accompanied by the sudden thickening of the lamellae at the crystal transformation temperature. These observations confirmed more thoroughly our previous prediction that the single crystal of trans-1, 4-polybutadiene, as formed, contains loose loops. The thickening phenomena and the change in the crystal transformation temperature of the trans-1,4-polybutadiene single crystal by heat treatment are also discussed from the thermodynamic viewpoint.     

Annealing of point defects in p-type germanium after electron irradiation at liquid nitrogen temperature

Annealing of radiation induced defects in p-type germanium was studied by measuring Hall coefficient and conductivity. The dopant was gallium or indium. It was concluded that the annealing stage between 80° and 140°K is caused by migration of the vacancy to the sink of an impurity atom. In this stage the vacancy migrates to a substitutional impurity atom and makes an association. The activation energy of the stage was found tO be 0.1 ev ad it is regarded to be that of the vacancy migration. The model for the annealing stage which occurs in the range 220 to 270°K is proposed as follows: An interstitial impurity atom migrates to a substitutional impurity atom and makes an association. From the activation energy of the stage, the migration energy of the interstitial impurity atom was concluded to be about 0.4 eV for gallium and 0.7 eV for indium atoms.     

Formation of an Imino‐Stabilized Cyclic Tin(II) Cation from an Amino(imino)stannylene

The novel amino(imino)stannylene 1 was prepared by conversion of HNIPr (NIPr=bis(2,6‐diisopropylphenyl)imidazolin‐2‐imino) with one equivalent of Lappert’s tin reagent (Sn[N(SiMe₃)₂]₂). Treatment of 1 with DMAP (4‐dimethylaminopyridine) yields its Lewis acid–base adduct 2 . The reaction of 1 with one equivalent of trimethylsilyl azide results in replacement of the amino group at the tin center by an N₃ substituent with concomitant elimination of N(SiMe₃)₃ to afford dimeric [N₃SnNIPr]₂ ( 3 ). Remarkably, the reaction of 1 with B(C₆F₅)₃ produces the novel tin(II) monocation 4 ⁺[MeB(C₆F₅)₃]^? comprising a four‐membered stannacycle through methyl‐abstraction from the trimethylsilyl group.     

Visualization of Heterogeneous Oxygen Storage Behavior in Platinum‐Supported Cerium‐Zirconium Oxide Three‐Way Catalyst Particles by Hard X‐ray Spectro‐Ptychography

The cerium density and valence in micrometer‐size platinum‐supported cerium–zirconium oxide Pt/Ce₂Zr₂O_x (x=7–8) three‐way catalyst particles were successfully mapped by hard X‐ray spectro‐ptychography (ptychographic‐X‐ray absorption fine structure, XAFS). The analysis of correlation between the Ce density and valence in ptychographic‐XAFS images suggested the existence of several oxidation behaviors in the oxygen storage process in the Ce₂Zr₂O_x particles. Ptychographic‐XAFS will open up the nanoscale chemical imaging and structural analysis of heterogeneous catalysts.     

Selective epitaxial growth by UHV-CVD using Si2H6 and Cl2

The conditions under which selective epitaxial growth (SEG) is achieved in UHV-CVD with Si₂H₆ are determined by the amount of Si₂H₆ molecules being supplied, and there is a critical gas supply amount (F_c) beyond which SEG will break down and lose its selectivity. The value of F_c is itself determined by two factors, growth temperature and the material used for masking, i.e. SiO₂, Si₃N₄. We found that this limiting factor of F_c was increased through the addition of a small amount of Cl₂, and that after such addition, the resulting decrease in growth rate is minimal.