Precipitation of Zinc Sulfide Particles from Homogeneous Solutions

Zinc sulfide particles were homogeneously precipitated by thermal decomposition of thioacetamide in acidic aqueous solutions in a one-step process. The influence of the operating conditions (initial concentration of zinc ion and TAA) on the nucleation time and number concentration of the generated particles was investigated. The experimental results show that the model of homogeneous nucleation previously developed and successfully tested for silver particle generation by a chemical reduction method can also be applied to the formation of zinc sulfide particles by homogeneous precipitation. Furthermore, in the particle formation method in which the nucleation time t* can be measured, the particle number concentration n* can be predicted by the simple relation n*=1/(4pir*Dt*) (r* is the critical nucleus radius, and D the monomer diffusion coefficient). Thus the particle number concentration can be easily predicted even if the rate expression and the critical supersaturation concentration are unknown. Copyright 2000 Academic Press.     

2‐Pyridone–tartronic acid (1/1), 3‐hydroxy­pyridinium hydrogen tartronate and 4‐hydroxy­pyridinium hydrogen tartronate

Tartronic acid forms a hydrogen‐bonded complex, C₅H₅NO·C₃H₄O₅, (I), with 2‐pyridone, while it forms acid salts, namely 3‐hydroxy­pyridinium hydrogen tartronate, (II), and 4‐hy­droxy­pyridinium hydrogen tartronate, (III), both C₅H₆NO⁺·C₃H₃O₅⁻, with 3‐hydroxy­pyridine and 4‐hydroxy­pyridine, respectively. In (I), the pyridone mol­ecules and the acid mol­ecules form R(8) and R(10) hydrogen‐bonded rings, respectively, around the inversion centres. In (II) and (III), the cations and anions are linked by N—H⋯O and O—H⋯O hydrogen bonds to form a hydrogen‐bonded chain. In each of (I), (II) and (III), an intermolecular hydrogen bond is formed between a carboxyl group and the hydroxyl group attached to the central C atom, and in (I), the hydroxyl group participates in an intramolecular hydrogen bond with a carbonyl group. No intermolecular hydrogen bond is formed between the carboxyl groups in (I), or between the carboxyl and carboxyl­ate groups in (II) and (III).     

Efficient Total Synthesis of Bongkrekic Acid and Apoptosis Inhibitory Activity of Its Analogues

Bongkrekic acid (BKA), isolated from the bacterium Burkholderia cocovenenans, is an inhibitor of adenine nucleotide translocator, which inhibits apoptosis, and is thus an important tool for the mechanistic investigation of apoptosis. An efficient total synthesis of BKA has been achieved by employing a three‐component convergent strategy based on Kocienski–Julia olefination and Suzuki–Miyaura coupling. It is noteworthy that segment B has been prepared as a new doubly functionalized coupling partner, which contributes to shortening of the number of steps. Torquoselective olefination with an ynolate has also been applied for the efficient construction of an unsaturated ester. Furthermore, it is revealed that 1‐methyl‐2‐azaadamantane N‐oxyl is an excellent reagent for final oxidation to afford BKA in high yield. Based on the total synthesis, several BKA analogues were prepared for structure–activity relationship studies, which indicated that the carboxylic acid moieties were essential for the apoptosis inhibitory activity of BKA. More easily available BKA analogues with potent apoptosis inhibitory activity were also developed.     

Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging

Terahertz (THz) time-domain spectroscopy and 3D THz pulsed imaging have been explored with regard to polymer materials, both commodity and historic polymers. A systematic spectroscopic study of a wide range of different polymer materials showed significant differences in their spectra. Polyolefins and polystyrenes generally exhibit lower absorption than other examined polymers, various cellulose derivates, poly(vinyl chloride), poly(methyl methacrylate), polyamide, hard rubber and phenol formaldehyde resin, the last of these exhibiting the most intense absorption over the entire range, 0.15–4.2 THz. It was also examined how the presence of plasticisers in poly(vinyl chloride), the presence of fillers in polypropylene, and the degree of branching in polyethylene and polystyrene affect the spectra; inorganic fillers in polypropylene affected the absorption most. With 3D THz pulsed imaging, features in polymer objects were explored, appearing either as integral parts of the material (coatings and pores in foams) or as a consequence of physical deterioration (cracks, delamination). All of these features of various complexities can be successfully imaged in 3D. Terahertz technology is thus shown to have significant potential for both chemical and structural characterisation of polymers, which will be of interest to heritage science, but also to the polymer industry and development of analytical technologies in general.     

Control on the Copper Valence and Properties by Oxygen Content Adjustment in the LaCuO3−ySystem (0≤y≤0.5)

The LaCuO_3−yperovskite is considered as the first member of the 01(n−1)nseries of “layered cuprates.” Highly oxidized, stoichiometric LaCuO₃is stabilized under very high oxygen pressures, and was synthesized in a cubic-anvil-type high-pressure apparatus at 5 GPa and 1400°C using excess amounts of KClO₄as an external oxidizing agent. Upon heating under ambient pressure the rhombohedral high-pressure phase loses oxygen yielding tetragonal, monoclinic, and orthorhombic forms of LaCuO_3−yas intermediate products before the final decomposition into La₂CuO₄and CuO or Cu₂O around 800°C. All three oxygen-deficient LaCuO_3−yphases could be isolated and their stability limits and corresponding oxygen contents conveniently investigated by annealing stoichiometric LaCuO₃in a thermobalance of high sensitivity in order toin situdetect the exact amount of oxygen loss. The nominal copper valence values calculated from the oxygen contents are compared and discussed with XPS data as well as with the results evaluated from magnetic susceptibility measurements.     

Network structure of fine silica particles

The network structure of silica aerogels heated at 300, 400 and 500°C in dried air have been determined by neutron total scattering measurements using a pulsed spallation neutron source. SANS experiments were also performed to obtain the particle size of the silica constituting aerogel. The elementary particle size obtained is about 13Å in diameter. The distances of the Si-O and O-O interactions in such fine silica particles are 1.61 and 2.64 Å, respectively, which are the same as those of fused silica. The coordination numbers of these pairs are found to be less evident than those of fused silica. In addition, the distances of the Si-Si pairs in the aerogels are slightly longer than that of fused silica. According to the heat treatment temperature, the coordination numbers of the Si-O and O-O interactions increase and the distance of the Si-Si pair decreases. These results indicate that although the network structure of fine silica particles treated at lower temperature is loose and imperfect, such structure can be changed by heating at relatively low temperature. The Raman spectra and the skeletal density measurements of the aerogels support also these results.     

Atomic structure of Al55(Cr1−xMnx)15Si30 metallic glasses observed by neutron diffraction

An atomic structure of Al₅₅(Cr_1−xMn_x)₁₅Si₃₀ (x = 0, 0.49,1) metallic glasses was studied by neutron diffraction. An advantage of the neutron diffraction technique was fully exploited by utilizing the negative scattering length of Mn to form a neutron zero scattering ‘alloy’ for the component Cr_0.51Mn_0.49 in this quaternary Al---(Cr, Mn)---Si alloy. This allows the atomic distribution of the resulting quasibinary Al---Si metallic glass to be derived directly. Moreover, the (Al, Si)---TM (TM = Mn, Cr) and TM---TM pair correlations were also extracted by taking appropriate linear combinations of the atomic structures for the Al₅₅(Cr_1−xMn_x)₁₅Si₃₀ (x = 0, 0.49, 1) metallic glasses. A sharp first peak in the (Al,Si) ---TM pair correlations thus obtained led to the conclusion that a strong attractive interaction exists between (Al, Si) and TM atoms and, hence, that the presence of the TM atoms is responsible for the formation of an amorphous phase.     

Observation of B-/+-->rho-/+rho0 decays

We report the first observation of the charmless vector-vector decay process B-/+-->rho(-/+)rho(0). The measurement uses a 78 fb(-1) data sample collected with the Belle detector at the KEKB asymmetric e(+)e(-) collider operating at the Upsilon(4S) resonance. We obtain a branching fraction of B(B-/+-->rho(-/+)rho(0))=[31.7+/-7.1(stat)+3.8-6.7(syst)]x10(-6). An analysis of the rho helicity-angle distributions gives a longitudinal polarization fraction of Gamma(L)/Gamma=0.95+/-0.11(stat)+/-0.02(syst). We also measure the direct-CP-violating asymmetry A(CP)(B-/+-->rho(-/+)rho(0))=0.00+/-0.22(stat)+/-0.03(syst).