twins in Mo-doped TiSi 2 thin films with the C54 structure

The defect structures in orthorhombic C54 crystallites in thin films of Mo-doped TiSi 2 produced by co-sputtering have been investigated by transmission electron microscopy. Almost all C54 crystallites contain a twin boundary parallel to (101), dividing a crystallite into two regions, each of which also contains many thin twins with the habit plane parallel to (001), which is inclined by about 45° from (101). Both of the two regions divided by the twin boundary parallel to (101) tend to have facets on (001) as well as thin twins with the habit plane parallel to (001). As a result, C54 crystallites exhibit a characteristic shape just like an oak leaf. While twins with the (001) habit plane have been observed in C54 crystallites in both binary and Mo-doped TiSi 2 thin films, those with the (101) habit plane are present only in Mo-doped TiSi 2 thin films. The twinning elements for (101) twins are determined to be K 1 = (101), , K 2 = (001) and m2 = [100]. The origin of (101) twins in Mo-doped TiSi 2 is discussed in terms of the change in the c / a axial ratio upon alloying TiSi 2 with Mo.     

The N = 16 Spherical Shell Closure in 24O

The unbound excited states of the most neutron-rich dripline oxygen isotope, ²⁴O, have been investigated by using the ²⁴O(p,p′)²⁴O^* reaction at the beam energy of 62 MeV/nucleon in inverse kinematics. The first and second unbound excited states of ²⁴O have been observed at ${E_{\rm x}= 4.63_{-0.14}^{+0.30}}$  MeV and ${E_{\rm x}= 5.13_{-0.24}^{+0.19}}$  MeV (preliminary) along with the evidence for another higher lying state at around 7.3 MeV. The quadrupole deformation parameter ${\beta_{2^+}}$ was deduced to be ${0.15_{-0.03}^{+0.08}}$ (preliminary) for the first time. The systematics of the ${\beta_{2^+}}$ and the ${E_{\rm x}(2_1^+)}$ in the Z = 8 isotopes shows the N = 16 spherical shell closure in ²⁴O.     

Tip‐heating‐assisted Raman spectroscopy at elevated temperatures

We demonstrate tip‐heating‐assisted enhanced Raman spectroscopy to investigate the temperature dependence of the carbon nanotube G‐band with nanoscale resolution. The controllable and nanoscale heat generated at the tip apex was used to thermally perturb and characterize a small volume in a carbon nanotube sample that is precisely positioned underneath the tip. The dependence of tip enhancement with temperature was also experimentally examined, which is in good agreement with the enhancement calculated from the electromagnetic model of isolated spheroids. The technique presented may open up opportunities in the study of controlled heat‐assisted biochemical reactions and physical transformations of nanostructures. It can also be used for thermal characterization of various materials requiring site‐selective and controllable nanoscale heat source and could enable the realization of new photothermal devices. Copyright © 2010 John Wiley & Sons, Ltd.     

TiC-MgO composite: an X-ray transparent and machinable heating element in a multi-anvil high pressure apparatus

ABSTRACT

TiC-MgO composite was developed as a heating element for X-ray study in the multi-anvil high pressure apparatus. We synthesized TiC-MgO blocks (50–70 wt.% of TiC) by compression in a cold isostatic press followed by baking in a gas flow furnace. Heaters of tubular shape were manufactured from the synthesized blocks either by lathe or numerically controlled milling machine. The so-produced heating elements have been proved to generate temperatures up to 2250?K at 10?GPa, condition where classical graphite heaters are not suitable anymore due to graphite-diamond transition. These new heaters have been successfully used for in situ X-ray radiography and diffraction measurements on liquid Fe alloys, exploiting excellent X-ray transparency.     

Synthesis,Structures, and Properties of Highly Strained Cyclophenylene–Ethynylenes with Axial and Helical Chirality

Single and double cyclophenylene–ethynylenes (CPEs) with axial and helical chirality have been synthesized by the Sonogashira cross-coupling of di- and tetraethynyl biphenyls with a U-shaped prearomatic diiodoparaphenylene followed by reductive aromatization. X-ray crystallographic analyses and DFT calculations revealed that the CPEs possess highly twisted bent structures. Bend angles on the edge of the paraphenylene units were close to the value of [5]cycloparaphenylene (CPP)—the smallest CPP to date. The double and single CPEs possessed stable chirality despite flexible biphenyl structures because of the high strain in the diethynyl–paraphenylene moiety. In both the single and double CPEs, orbital interactions along the biphenyl axis were observed by DFT calculations in LUMO and LUMO+2 of the single CPE and LUMO+1 of the double CPE, which likely cause lowering of these orbital energies. Concerning chiroptical properties: boosting of the g_abs value was observed in the biphenyl-based double CPE, as well as the binaphthyl-based single CPE, compared to the biphenyl-based single CPE.     

Stable meso‐Aryl β‐Alkyl Hybrid Sapphyrin with a Warped π‐Conjugation Circuit and Neo‐Confused Sapphyrin–Silver(I) Complex

A meso‐aryl and β‐alkyl substituted sapphyrin and its rhodium(I) and silver complexes were synthesized. This sapphyrin was so stable that the non‐inverted and warped structure could be analyzed by X‐ray crystallography even in its neutral state. Its bis‐rhodium(I) complex has a more planar structure than the sapphyrin with enhanced aromaticity over the conjugation circuit. On the other hand, silver metalation of the sapphyrin caused a marked core rearrangement into a neo‐confused sapphyrin derivative with a C(α)?N bond and a twisted macrocycle.     

Fructose/dioxygen biofuel cell based on direct electron transfer-type bioelectrocatalysis

One-compartment biofuel cells without separators have been constructed, in which d-fructose dehydrogenase (FDH) from Gluconobacter sp. and laccase from Trametes sp. (TsLAC) work as catalysts of direct electron transfer (DET)-type bioelectrocatalysis in the two-electron oxidation of d-fructose and four-electron reduction of dioxygen as fuels, respectively. FDH adsorbs strongly and stably on Ketjen black (KB) particles that have been modified on carbon papers (CP) and produces the catalytic current with the maximum density of about 4 mA cm(-2) without mediators at pH 5. The catalytic wave of the d-fructose oxidation is controlled by the enzyme kinetics. The location and the shape of the catalytic waves suggest strongly that the electron is directly transferred to the KB particles from the heme c site in FDH, of which the formal potential has been determined to be 39 mV vs. Ag|AgCl|sat. KCl. Electrochemistry of three kinds of multi-copper oxidases has also been investigated and TsLAC has been selected as the best one of the DET-type bioelectrocatalyst for the four-electron reduction of dioxygen in view of the thermodynamics and kinetics at pH 5. In the DET-type bioelectrocatalysis, the electron from electrodes seems to be transferred to the type I copper site of multi-copper oxidases. TsLAC adsorbed on carbon aerogel (CG) particles with an average pore size of 22 nm, that have been modified on CP electrodes, produces the catalytic reduction current of dioxygen with a density of about 4 mA cm(-2), which is governed by the mass transfer of the dissolved dioxygen. The FDH-adsorbed KB-modified CP electrodes and the TsLAC-adsorbed CG-modified CP electrodes have been combined to construct one-compartment biofuel cells without separators. The open-circuit voltage was 790 mV. The maximum current density of 2.8 mA cm(-2) and the maximum power density of 850 microW cm(-2) have been achieved at 410 mV of the cell voltage under stirring.     

Hydrogen encapsulation in a silicon clathrate type I structure: Na5.5(H2)2.15Si46: synthesis and characterization

A hydrogen-encapsulated inorganic clathrate, which is stable at ambient temperature and pressure, has been prepared in high yield. Na5.5(H2)2.15Si46 is a sodium-deficient, hydrogen-encapsulated, type I silicon clathrate. It was prepared by the reaction between NaSi and NH4Br under dynamic vacuum at 300 degrees C. The Rietveld refinement of the powder X-ray diffraction data is consistent with the clathrate type I structure. The type I clathrate structure has two types of cages where the guest species, in this case Na and H2, can reside: a large cage composed of 24 Si, in which the guest resides in the 6d crystallographic position, and a smaller one composed of 20 Si, in which the guest occupies the 2a position. Solid-state 23Na, 1H, and 29Si MAS NMR confirmed the presence of both sodium and hydrogen in the clathrate cages. 23Na NMR shows that sodium completely fills the small cage and is deficient in the larger cage. The 1H NMR spectrum shows a pattern consistent with mobile hydrogen in the large cage. 29Si NMR spectrum is consistent with phase pure type I clathrate framework. Elemental analysis is consistent with the stoichiometry Na5.5(H2.15)2Si46. The sodium occupancy was also examined using spherical aberration (Cs) corrected scanning transmission electron microscopy (STEM). The high-angle annular dark-field (HAADF) STEM experimental and simulated images indicated that the Na occupancy of the large cage, 6d sites, is less than 2/3, consistent with the NMR and elemental analysis.     

Chemistry of tantalum clusters in solution and on SiO2 supports: analogies and contrasts

Tantalum clusters have been synthesized from Ta(CH2Ph)5 on the surface of porous fumed SiO2. When these clusters are small, incorporating, on average, several Ta atoms, their chemistry is similar to that of molecular tantalum clusters (and other early transition-metal) clusters. For example, The Ta-Ta bonds in these small supported clusters have been characterized by extended X-ray absorption fine structure (EXAFS), IR, and UV-vis spectroscopy, being similar to those in molecular analogues. The redox reactions of the supported clusters, characterized by X-ray absorption near-edge structure, are analogous to those of early transition-metal clusters in solution. In contrast to the largest of these clusters in solution and in the solid state, those supported on SiO2 are raftlike, facilitating the substantial metal-support-oxygen bonding that is evident in the EXAFS spectra. Samples consisting of tantalum clusters on SiO2 catalyze alkane disproportionation and the conversion of methane with n-butane to give other alkanes, but catalytic properties of analogous clusters in solution have barely been explored.     

DNA oligomers having a diazapyrenium dication (DAP2+); synthesis and DNA cleavage activities.

Aiming at the creation of functionalized antisense DNA oligomers possessing site-selective DNA cleaving activity, viologen and a related compound, diazapyrenium dication (DAP2+), were selected and introduced into oligodeoxyribonucleotides as a functionalized molecule. The conjugation of these functionalized molecules with DNA proceeded smoothly by using standard H-phosphonate chemistry. A part of the DAP(2+)-tethered DNA oligomers was synthesized by a combination of solid support method and liquid phase technique. Viologen-tethered DNA oligomers showed no significant activity toward DNA cleavage in spite of their characteristic ESR spectra. On the other hand, it was observed that the DAP(2+)-tethered DNA oligomers formed more stable duplexes with their complementary strands than the corresponding wild type, and these molecules effectively cleaved the complementary strands at the specific site of 2-3 bases away from the modified phosphoramidate linkage. The effect of position and length of the linker arm on the selectivity in the cleavage reaction was also investigated, and it was found that introduction at the 3'- or 5'-end phosphate site is more favorable, probably due to duplex stabilization.