Tunneling-current-induced light emission from individual carbon nanotubes

Tunneling electrons from a scanning tunneling microscope were used to excite light emission from individual multiwalled carbon nanotubes adsorbed on a highly ordered pyrolytic graphite surface. In the integral photon-intensity map, spatially uniform emission in the visible region was observed along the identical multiwalled carbon nanotubes. The emission spectra for the individual nanotubes showed unique profiles which differed with each nanotube, and were classified into two types. Our results indicate that the light emission is due to not the localized electronic states at the tube ends or defects but radiative transitions of electrons between the one-dimensional van Hove singularities, indicating that the two types of spectra are attributed to metallic and semiconducting nanotubes.     

Development of an on-line low gas pressure cell for laser ablation-ICP-mass spectrometry.

An on-line low gas pressure cell device has been developed for elemental analysis using laser ablation-ICP-mass spectrometry (LA-ICPMS). Ambient gas in the sample cell was evacuated by a constant-flow diaphragm pump, and the pressure of the sample cell was controlled by changing the flow rate of He-inlet gas. The degree of sample re-deposition around the ablation pit could be reduced when the pressure of the ambient gas was lower than 50 kPa. Produced sample aerosol was drawn and taken from the outlet of the diaphragm pump, and directly introduced into the ICP ion source. The flow rate of He gas controls not only the gas pressure in the sample cell, but also the transport efficiency of the sample particles from the cell to the ICP, and the gas flow rate must be optimized to maximize the signal intensity of the analytes. The flow rates of the He carrier and Ar makeup gas were tuned to maximize the signal intensity of the analytes, and in the case of (238)U from the NIST SRM610 glass material, the signal intensity could be maximized with gas flow rates of 0.4 L/min for He and 1.2 L/min for Ar. The resulting gas pressure in the cell was 30 - 35 kPa. Using the low gas pressure cell device, the stability in the signal intensities and the resulting precision in isotopic ratio measurements were evaluated. The signal intensity profile of (63)Cu obtained by laser ablation from a metallic sample (NIST SRM976) demonstrated that typical spikes in the transient signal, which can become a large source of analytical error, were no longer found. The resulting precision in the (65)Cu/(63)Cu ratio measurements was 2 - 3% (n = 10, 2SD), which was half of the level obtained by laser ablation under atmospheric pressure (6 - 10%). The newly developed low-pressure cell device provides easier optimization of the operational conditions, together with smaller degrees of sample re-deposition and better stability in the signal intensity, even from a metallic sample.     

Quantitative Evaluation of Oxygenation and Metabolism in the Human Skeletal Muscle

The forearm muscles of five healthy males were monitored for changes in microvessel hemoglobin saturation (SO_2-TRS) by near infrared time-resolved spectroscopy (NIR_TRS) and changes in phosphorus metabolites by magnetic resonance spectroscopy (³¹P-MRS) during 12 min of resting arterial occlusion. Muscle oxygenation and phosphorus metabolites were also measured during grip exercises at varying intensities. Upon the initiation of occlusion, SO_2-TRS fell progressively until it reached a plateau in the latter half of the occlusion. Phosphocreatine (PCr) began to decrease around 6 min after the initiation of arterial occlusion. The resting O₂ store and O₂ consumption were 295 μM and 0.95 μM/sec, respectively-values which reasonably agree with the reported results. A significant correlation was observed between the changes in SO_2-TRS and PCr during exercise (r² = 0.80, p < 0.001). These results indicate that NIR_TRS is able to provide reliable information about resting metabolism and oxidative rate during exercise. NIR_TRS and MRS are useful to monitor oxygenation and energetics noninvasively in the human muscle.     

Tandem Time-of-Flight Mass Spectrometer with High Precursor Ion Selectivity Employing Spiral Ion Trajectory and Improved Offset Parabolic Reflectron

In this study, we have developed a tandem time-of-flight mass spectrometry (TOF/TOF) technique involving the use of a matrix-assisted laser desorption/ionization ion source that exhibits high precursor ion selectivity. An ion optical system with a 17 m spiral ion trajectory was used in the first time-of-flight mass spectrometer. High precursor ion selectivity was achieved by realizing a 15 m flight path, which is considerably longer than that of the conventional MALDI-TOF/TOF before the precursor ion selection by an ion gate; monoisotopic ions could be selected properly up to m/z 2500. Furthermore, the first time-of-flight mass spectrometer was composed of electrostatic sectors and could eliminate post-source decay (PSD) ions. Precursor ions with 20 keV kinetic energy were selected and injected into a collision cell, leading to the generation of fragment ions by high-energy collision-induced dissociation (HE-CID). The optimized second time-of-flight mass spectrometer included a post-acceleration region and an offset parabolic reflectron to record product ion spectra in the entire mass range. Our system could generate a simple HE-CID product ion spectrum because each fragment pathway could be observed as a single peak by the selection of monoisotopic ions of all precursor ions and HE-CID fragment pathways could be predominantly observed by the PSD ion elimination.     

Dual modification of a triple-stranded β-helix nanotube with Ru and Re metal complexes to promote photocatalytic reduction of CO2

We have constructed a robust β-helical nanotube from the component proteins of bacteriophage T4 and modified this nanotube with Ru(II)(bpy)(3) and Re(I)(bpy)(CO)(3)Cl complexes. The photocatalytic system arranged on the tube catalyzes the reduction of CO(2) with higher reactivity than that of the mixture of the monomeric forms.     

Incorporation of organometallic Ru complexes into apo-ferritin cage

Spherical protein cages such as an iron storage protein, ferritin, have great potential as nanometer-scale capsules to assemble and store metal ions and complexes. We report herein the synthesis of a composite of an apo-ferritin cage and Ru(p-cymene) complexes. Ru complexes were efficiently incorporated into the ferritin cavity without degradation of its cage structure. X-Ray crystallography revealed that the Ru complexes were immobilized on the interior surface of the cage mainly by the coordination of histidine residues.     

Theoretical study of oxidation of cyclohexane diol to adipic anhydride by [Ru(IV)(O)(tpa)(H2O)]2+ complex (tpa ═ tris(2-pyridylmethyl)amine)

The catalytic conversion of 1,2-cyclohexanediol to adipic anhydride by Ru(IV)O(tpa) (tpa ═ tris(2-pyridylmethyl)amine) is discussed using density functional theory calculations. The whole reaction is divided into three steps: (1) formation of α-hydroxy cyclohexanone by dehydrogenation of cyclohexanediol, (2) formation of 1,2-cyclohexanedione by dehydrogenation of α-hydroxy cyclohexanone, and (3) formation of adipic anhydride by oxygenation of cyclohexanedione. In each step the two-electron oxidation is performed by Ru(IV)O(tpa) active species, which is reduced to bis-aqua Ru(II)(tpa) complex. The Ru(II) complex is reactivated using Ce(IV) and water as an oxygen source. There are two different pathways of the first two steps of the conversion depending on whether the direct H-atom abstraction occurs on a C-H bond or on its adjacent oxygen O-H. In the first step, the C-H (O-H) bond dissociation occurs in TS1 (TS2-1) with an activation barrier of 21.4 (21.6) kcal/mol, which is followed by abstraction of another hydrogen with the spin transition in both pathways. The second process also bifurcates into two reaction pathways. TS3 (TS4-1) is leading to dissociation of the C-H (O-H) bond, and the activation barrier of TS3 (TS4-1) is 20.2 (20.7) kcal/mol. In the third step, oxo ligand attack on the carbonyl carbon and hydrogen migration from the water ligand occur via TS5 with an activation barrier of 17.4 kcal/mol leading to a stable tetrahedral intermediate in a triplet state. However, the slightly higher energy singlet state of this tetrahedral intermediate is unstable; therefore, a spin crossover spontaneously transforms the tetrahedral intermediate into a dione complex by a hydrogen rebound and a C-C bond cleavage. Kinetic isotope effects (k(H)/k(D)) for the electronic processes of the C-H bond dissociations calculated to be 4.9-7.4 at 300 K are in good agreement with experiment values of 2.8-9.0.     

Fabrication and evaluation of ZnO nanorods by liquid-phase deposition

The ZnO nanorod growth mechanism during liquid-phase deposition (LPD) has been investigated, with results considered in the context of phase stabilization, LPD chemical processes, and Gibbs free energy and entropy. Zinc oxide (ZnO) possesses unique optical and electronic properties, and obtaining ZnO species with high specific surface area is important in ZnO applications. Highly c-axis-oriented ZnO films are expected to be utilized in future optical and electrical devices. ZnO nanorods were synthesized using an aqueous solution deposition technique on a glass substrate with a free-standing ZnO nanoparticle layer. ZnO nanorod growth was easily controlled on the nanoscale by adjustment of the immersion time (15-210 min). X-ray diffraction, field-emission scanning electron microscopy (FE-SEM), and film thickness measurements were used to characterize the crystalline phase, orientation, morphology, microstructure, and growth mechanism of the ZnO nanorods. FE-SEM images were analyzed by image processing software, which revealed details of the of ZnO nanorod growth mechanism.     

Extracellular Production and Characterization of Two <Emphasis Type="Italic">Streptomyces</Emphasis><Emphasis Type="SmallCaps">l</Emphasis>-Asparaginases

l-Asparaginase (ASNase) has proved its use in medical and food industries. Sequence-based screening showed the thermophilic Streptomyces strain Streptomyces thermoluteus subsp. fuscus NBRC 14270 (14270 ASNase) to positive against predicted ASNase primary sequences. The 14270 ASNase gene and four l-asparaginase genes from Streptomyces coelicolor, Streptomyces avermitilis, and Streptomyces griseus (SGR ASNase) were expressed in Streptomyces lividans using a hyperexpression vector: pTONA5a. Among those genes, only 14270 ASNase and SGR ASNase were successful for overexpression and detected in culture supernatants without an artificial signal peptide. Comparison of the two Streptomyces enzymes described above demonstrated that 14270 ASNase was superior to SGR ASNase in terms of optimum temperature, thermal stability, and pH stability.     

Photoluminescence of samarium-doped TiO2 nanotubes

Samarium (Sm)-modified TiO₂ nanotubes (TNTs) were synthesized by low-temperature soft chemical processing. X-ray powder diffraction analyses of the synthesized Sm-doped and non-doped TNTs show a broad peak near 2θ=10°, which is typical of TNTs. The binding energy of Sm ³d_5/2 for 10 mol% Sm-doped TNT (1088.3 eV) was chemically shifted from that of Sm₂O₃ (1087.5 eV), showing that Sm existed in the TiO₂ lattice. Sm-doped TNTs clearly exhibited red fluorescence, corresponding to the doped Sm³⁺ ion in the TNT lattice. The Sm-doped TNT excitation spectrum exhibited a broad curve, which was similar to the UV–vis optical absorption spectrum. Thus, it was considered that the photoluminescence emission of Sm³⁺-doped TNT with UV-light irradiation was caused by the energy transfer from the TNT matrix via the band-to-band excitation of TiO₂ to the Sm³⁺ ion.