Diamond-like carbon films prepared by pulsed-laser evaporation

Diamond-like carbon thin films were prepared by pulsed-laser evaporation. In this method a carbon target was irradiated by a XeCl laser with a power density of 3×10⁸ W/cm² and carbon atoms, together with a small number of ions, were produced. Deposition rates and film properties changed sensitively with substrate temperature. The films deposited at 50°C were diamond-like, having reasonable hardness, high refractive index (2.1–2.2 at 633 nm), optical transparency in the infrared, electrical resistivity of 10⁸ cm and chemical inertness (no dissolution in a HFHNO₃ solution). The band gap measured from optical absorption was 1.4 eV. Raman spectrum and infrared absorption, whose features varied with the substrate temperature, were also measured. The films were amorphous and no crystallinity was observed, as confirmed by x-ray diffraction, transmission electron diffraction and Raman spectroscopy. Hydrogen atoms were incorporated in the films with a typical H/C ratio of 0.3. The application of a negative bias to the substrate modified the deposition due to the presence of ions.     

Crystal structures and Mössbauer spectroscopic studies of oxo-centered trinuclear chloroacetate complexes

The crystal structures of oxo-centered trineclear cobalt-iron chloroacetate complex [Co^IIFe ₂ ^III O(CH₂ClCO₂)₆(H₂O)₃]·3H₂O (1) was compared with that of previously reported trinuclear iron complex [Fe^IIFe ₂ ^III O(CH₂ClCO₂)₆(H₂O)₃]·3H₂O (2) which has an isomorphous structure to 1. Compound 1 crystallizes in space group P2₁/n with Z=4 in a unit cell of a=14.826 (4) Å, b=4.536 (8) Å, c=14.000 (4) Å, =100.32 (2)⁰ and V=2968 (11) ų. The structure was refined to R=0.75 and R_w=0.82. The coordination geometries of the three iron atoms are observed equivalent in 1 indicating a static disorder of the position among cobalt and iron atoms. Two distinct Fe^III doublets observed in Mössbauer spectra of 1 become an indistinguishable broad doublet by dehydration of crystal water. On the other hand, no significant line-broadening is observed after the dehydration in complex 2. The results indicate that the dehydration in 2 induces a local environmental change reordering of an electronic configuration around iron atoms, whereas the remaining disordering is reflected in Mössbauer spectrum after the dehydration in 1.     

Medium-sized cyclophanes—XVII : Tetra-, hexa-, octa- and decahydropyrenes from [2.2]metacyclophane. Transannular dehydrogenation,isomerization, and disproportionation reactions by means of benzoyl peroxide,metal salts and sulfuric acids

[2.2]Metacyclophane (1) undergoes a variety of reactions according to the reagents and conditions. These include (1) substitution (path a), (2) transannular dehydrogenation (path b and c), (3) cycloisomerization (path d) and (4) transannular hydrogenation. A brief summary of these reactions is presented.The diversity of the reactions of 1 is further explored using benzoyl peroxide (BPO), cupric chloride, aluminum chloride, other metal salts, H₂SO₄ and FSO₃H. With BPO or cupric chloride, one-electron transfer mechanism is postulated. This involves a tautomeric ion pair formed by the intramolecular arylation with an aryl cation radical. A supporting evidence in favor of the mechanism is presented from experiments using various metal salts in different solvents.On the contrary, the reaction with aluminum chloride gives decahydropyrene (8) and octahydropyrene (11) together with cycloisomerization product 5 and dehydrogenation products 2, 3 and 4. When treated with AlCl₃HCl 1 gives similar products as above but the product ratios are quite different. The major product is 5 but only a trace amount of 8 is formed. The reaction with H₂SO₄ or FSO₃H also produce 2, 4, 5 and 11. Some mechanistic evidence in favor of the disproportionation reaction is presented.     

Multielement determination in tobacco leaves by photon activation analysis

A nondestructive photon activation procedure with 30 MeV bremsstrahlung followed by high-resolution gamma-spectrometry has been applied to the multielement determination in tobacco leaves and commercial cigarettes. The elements determined by this method included essential minor elements such as Ca, Cl, K and Mg, essential trace elements such as Fe, Mn and Zn, and possibly toxic elements such As and Sb. The NBS Orchard Leaves could successfully be used as a comparative standard. The method is quite simple and gives good reproducible results for at least 12 elements.     

Scalar auxiliary variable approach for conservative/dissipative partial differential equations with unbounded energy functionals

BIT Numerical Mathematics - In this paper, we present a novel investigation of the so-called SAV approach, which is a framework to construct linearly implicit geometric numerical integrators for...     

Crystal and molecular structure of 6-0-acetylgrayanotoxin III

The crystal and molecular structure of a grayanotoxin III derivative, 6-0-acetylgrayanotoxin III is presented. The crystal is orthorhombic, space group P2₁2₁2₁, witha=15.582(3),b=21.304(3),c=6.339(3)Å,V=2104(1) ų Z=4. The structure was solved by direct methods and refined by full matrix least-squares methods to a finalR=0.047 for 1763 independent reflections withF ₀>3 (F ₀) The molecule is based on a tetracyclic structure consisting of two five-membered, one six-membered, and one seven-membered ring with various conformations.