Luminescence channels of manganese-doped spinel

Two independent luminescence channels are observed from manganese-doped spinel Mn:MgAl₂O₄. The luminescence around 520 nm is assigned to transition from the lowest electronic excited state ⁴T₁ to the ground state ⁶A₁ of Mn²⁺ (3d)⁵ ion by analyzing the excitation spectrum and electron spin resonance measurement. The emission at 650 nm is triggered by the band edge excitation and is assigned similarly to the charge-transfer process associated with the manganese ion.     

Influences of Si pillar geometry on SiN-stressor induced local strain

The local strains in Si pillars induced by SiN stressors were quantitatively investigated as a function of geometry by micro-Raman scattering spectroscopy. Raman shifts of a cantilever microstructure were twice as large as those of a bridge microstructure. This difference was due to the different dimensions of the strains, i.e., biaxial strains in the cantilever type and uniaxial strains in bridge type. The thermal stability of the SiN stressor was also investigated. The results showed induced strains were stable after post-annealing at high temperature (∼1000 °C).     

Structural changes in poly(L-alanine) induced by heat treatment

Structural changes in poly(L -alanine)(PLA), a model compound related to tussah silk fibroin, induced by heat treatment have been studied by differential thermal analysis, x-ray diffraction, and infrared spectroscopy. PLA heated below 300°C shows x-ray patterns very similar to those of the α-helix crystalline phase, in addition to the diffraction patterns due to the β structure. Samples heated at 368°C exhibit predominantly the diffraction patterns due to the β crystalline phase. From infrared spectra, PLA samples heated below 280°C are found to be composed of all three molecular conformations: β sheet, random coil, and α helix. The intensity of the infrared absorption at 650 cm^?1 (amide V) assigned to the random coil conformation is decreased by heat treatment above 325°C. The content of the β-sheet structure remains almost constant when the specimen is heated below 325°C, and increases abruptly on heating to around 335°C, while the random coil content is decreased abruptly by heat treatment above 335°C. The α-helix content does not change, regardless of heat treatment. It is suggested therefore that the random coil conformation of PLA transforms directly into the β sheet on heat treatment above 335°C.     

Substitution of both chloro and sulfinyl groups of aryl 1-chlorocyclopropyl sulfoxides in one-pot via cyclopropylmagnesium carbenoids: a synthesis of multi-substituted cyclopropanes

The rearrangement of cyclopropylmagnesium carbenoids, which were generated from aryl 1-chlorocyclopropyl sulfoxides with a Grignard reagent, to allenes was found to be suppressed by adding HMPA as an additive. Alkylation of the cyclopropylmagnesium carbenoids with the Grignard reagent gives mainly alkylated cyclopropylmagnesium chloride instead. The cyclopropylmagnesium chloride intermediate can be trapped with several electrophiles to afford multi-substituted cyclopropanes. This procedure provides a new method for a synthesis of multi-substituted cyclopropanes.     

Magnetic circular dichroism study of directly fused porphyrins.

The magnetic circular dichroism (MCD) spectra of doubly and triply linked fused bisporphyrins (2MD and 2MT, M = Ni, Zn, Cu, Pd, and H2) and triply linked higher oligomers (3ZnT and 4ZnT) have been measured, and their Q-bands assigned based on the results of INDO/s calculations. In contrast to the Faraday A term observed for the Q(0,0) band of Ni(II) tetraphenylporphyrin, a single positive Faraday B term was observed for the lowest energy transition of the fused systems. The calculations indicated that the molecular orbitals (MOs) of the directly fused porphyrins consist of linear combinations of the constituent monomeric MOs, and that the effect of lowering the symmetry is always larger on the lowest unoccupied molecular orbital (LUMO) than on the highest occupied molecular orbital (HOMO). On the basis of Michl's perimeter model, these features can be correlated with the observed positive MCD signs in the near infrared region. A weak absorption band at 600-700 nm for the fused dimers can be assigned to a short-axis polarized Q transition.     

Pulsed laser deposition of pure fluoroapatite film without OH groups

The relation between O₂ pressure and composition in the pulsed‐laser deposition of fluoroapatite was investigated using both on‐axis and off‐axis methods to determine the optimal conditions for obtaining a pure fluoroapatite film without OH groups. Through this, it was found that an O₂ pressure of 10 Pa, combined with an off‐axis method, results in P/Ca and F/Ca values (0.6 and 0.2, respectively) that match closely with a stoichiometric composition of Ca₁₀(PO₄)₆F₂. Fourier transform infrared spectroscopy analysis confirmed that this optimized film was almost pure fluoroapatite, with no evidence of any OH groups originating from hydroxyapatite. X‐ray diffraction also revealed that this fluoroapatite film crystallizes with a c‐axis orientation perpendicular to its surface.     

Homoleptic Zincate‐Promoted Room‐Temperature Halogen–Metal Exchange of Bromopyridines

Homoleptic lithium tri‐ and tetraalkyl zincates were reacted with a set of bromopyridines. Efficient and chemoselective bromine–metal exchanges were realized at room temperature with a substoichiometric amount of nBu₄ZnLi₂?TMEDA reagent (1/3 equiv; TMEDA=N,N,N′,N′‐tetramethylethylenediamine). This reactivity contrasted with that of tBu₄ZnLi₂?TMEDA, which was inefficient below one equivalent. DFT calculations allowed us to rationalize the formation of N???Li stabilized polypyridyl zincates in the reaction. The one‐pot difunctionalization of dibromopyridines was also realized using the reagent stoichiometrically. The direct creation of C? Zn bonds in bromopyridines enabled us to perform efficient Negishi‐type cross‐couplings.