Chemistry of organosilicon compounds: CIV. Syntheses of novel organoelement heterocycles containing titanium and silicon

Four new dicyclopentadienyltitanium(IV) metallocycles, Cp₂TiCH₂XCH₂ (X = SiMe₂OSiMe₂, SiMe₂CH₂SiMe₂, SiMe₂SiMe₂, and SiMe₂SiMe₂SiMe₂) are prepared and characterized.     

Measurement of Fluorescence Quantum Yield of Ultraviolet-Absorbing Substance Extracted from Red Alga: Porphyra yezoensis and its Photothermal Spectroscopy

Optical properties of an ultraviolet-absorbing substance (UVAS) extracted from the marine red alga, Porphyra yezoensis, have been investigated. The substance is excited by UV light, and the emitted fluorescence is detected using an intelligent fluorescence detector. The fluorescence of UVAS is weaker by four orders of magnitude than the fluorescence intensity emitted by anthracene in the same optical system. The absorbed energy is apparently not transferred to the photosynthesis process and is believed to be consumed as heat. Using photothermal spectroscopy, a signal is observed indicating that the absorbed photon energy has transferred to the heat. The waveform of the photothermal signal of UVAS is similar to that of quinoxaline, whose fluorescence quantum yield is known to be zero. It is determined that the fluorescence quantum yield and the energy of the triplet state of UVAS are 1.7 ± 0.7 ± 10⁻⁴ and 21000 ± 1000 cm ⁻¹, respectively. The conclusion is that the excited molecules of UVAS decay by passing through the triplet state and dissipate all absorbed energy as heat.     

Solvent-induced morphological change of microporous hollow fiber membranes

Microporous polyethylene hollow fiber membranes (EHF-1 and EHF-2) were subjected to solvent treatment, and the effects of this treatment on membrane morphology and permeating properties were studied. Membranes treated with various organic solvents exhibited enhanced permeability, enlarged pore size, and increased shrinkage in the longitudinal direction. These phenomena were found to depend on the surface tension of the solvent: the higher the surface tension of the solvent, the larger the change in morphology and permeation of the membrane. A mechanism to account for the effects of solvent treatment on the morphology of the membrane is proposed taking into consideration the influence of the type of solvent used for treatment. The enhanced morphological and permeation changes are ascribed to the formation of liquid bridges between two microfibrils of the membrane during drying followed by the deformation and adhesion of the adjacent microfibrils based on the surface tension of the solvent.     

Scanning tunneling microscopy of N2H4 on silicon surfaces

The chemistry of N₂H₄ on Si(100)2 × 1 and Si(111)7 × 7 has been studied using scanning tunneling microscopy. At low coverages on Si(100)2 × 1 at room temperature the adsorption sites are distributed randomly on the surface and are imaged as dark spots in the dimer row by the STM. Upon annealing the substrate at 600 K, both isolated reaction products, as well as clusters of reaction products are formed on the surface. The STM images show that the majority of the isolated reaction products are adsorbed symmetrically across the dimers. Based on previous HREELS data, these are most likely NH_x groups. However, the clusters are not well resolved. Because of this we speculate that they are not simply symmetrically adsorbed NH_x groups, but likely have a more complicated internal structure. At higher coverages, the STM images show that the predominant pathway for adsorption is with the N---N bond parallel to the surface, in agreement with HREELS studies of this system. On Si(111)7 × 7, the molecule behaves in a manner which is similar to NH₃. That is, at low coverages the molecule adsorbs preferentially at center adatoms due to the greater reactivity of these sites, while at higher coverages it also reacts with the corner adatoms.     

Interaction of hydrogen fluoride with ruthenium tetroxide

In the course of the studies concerning hydrolysis of ruthenium fluorides and fluorination of ruthenium hydroxides, we frequently noticed the formation of a volatile substance which showed a strong absorption band at 1030 cm^?1. We pursued this unknown substance and found that it was an adduct between ruthenium tetroxide and hydrogen fluoride:

This new adduct, RuO₄(HF)₁₀, is observable at temperature higher than 0°C and at HF pressure greater than 150 mmHg. Between 4000 and 200 cm^?1, the adduct shows two absorption bands—1030 cm^?1 and 389 cm^?1. At 0°C, the adduct in the gas-phase disappears for condensation.On the basis of these results, credibility of the earlier literature on RuF₈ was discussed.