Formation and characterization of emulsions using beta-cyclodextrin as an emulsifier

The preparation and characterization of n-alkane/water emulsions using beta-cyclodextrin (beta-CD) were studied. The prepared n-alkane/water emulsions were of the oil-in-water (O/W) type, and the stability of emulsions was in the order of n-hexadecane > n-dodecane > n-octane. From observations using polarized light microscopy and powder X-ray diffraction measurement, it was suggested that the formation of a dense film at the oil-water interface and the three-dimensional structural network created by precipitated complexes in the continuous phase are associated with the stability of emulsion. Furthermore, it was clarified that O/W-type emulsions were formed because the contact angle (theta ow) which the precipitate makes with the interface was theta ow < 90 degrees in all compounds (oils) used in this study.     

Identification of oxidation states of metal oxides by MALDI-TOF MS

For the detection of inorganic species, we have developed chemical reaction laser desorption ionization mass spectrometry, and applied it to the analysis of metal oxides in different oxidation states. Metal oxide species insoluble in common organic solvents were finely grounded in a mortar and suspended in a solvent. The turbid suspension was placed on a sample holder on which a suitable chelating reagent had been previously spotted in a similar manner for sample preparation employed in the matrix-assisted laser desorption mass spectrometry (MALDI-MS). By using this method, the mass spectra of manganese (II and IV) oxides (MnO and MnO₂), cobalt (II and III) oxides (CoO and Co₂O₃), and chromium (III and VI) oxides (Cr₂O₃ and CrO₃) were successfully obtained. By adjusting the experimental conditions, such as ionization modes and chelating reagents, the non-identical mass spectra were obtained for the elements in the different oxidation state. Thus, the oxidation states could be identified clearly.     

Terahertz time-domain attenuated total reflection spectroscopy in water and biological solution

We demonstrate time-domain attenuated total reflection spectroscopy in terahertz frequency region. Geometry of the reflection measurement is well optimized to obtain accurate optical constants of water or aqueous biomolecular system. We determine the dielectric constants of distilled water and sucrose solutions with this technique. This technique will open new aspects in the research field of biological systems in water.     

A dinuclear MnIII-CuII single-molecule magnet

The reaction of 1/3 equivalent of CuCl2.2H2O with MnCl2.4H2O and 5-bromo-2-salicylideneamino-1-propanol (H(2)5-Br-sap) in methanol gave dark brown crystals of [MnIIICuIICl(5-Br-sap)2(MeOH)] (1). Complex 1 has an alkoxo-bridged dinuclear core of MnIII and CuII ions, which have elongated octahedral and square-planar coordination geometries, respectively. In dc magnetic susceptibility measurements, chi(m)T values increased as the temperature was lowered, followed by a sudden decrease below 20 K. This behavior is indicative of the occurrence of intramolecular ferromagnetic interactions, and fitting gave an S=5/2 spin ground state with an exchange coupling constant J(MnCu) of +78 cm(-1). Magnetization data collected as a function of temperature and applied magnetic field were analyzed by using a spin Hamiltonian with isotropic Zeeman and axial zero-field splitting (ZFS) terms, and a negative D(5/2) value (-1.86 cm(-1)) was obtained. A high-field EPR (HFEPR) spectrum (342.0 GHz) at 4.2 K was composed of four peaks, and two additional peaks at higher magnetic field appeared as the temperature was increased. The temperature dependences in the HFEPR spectra are indicative of a negative D(5/2) value, and fitting of the data gave D(5/2)=-1.81 cm(-1). In the ac magnetic susceptibility measurements, frequency dependent in-phase (chi(m)') and out-of-phase (chi(m)') signals with peak maxima at 0.7-1.5 K were observed and small peaks below 0.7 K appeared. The ac susceptibility data supports that 1 is a single-molecule magnet (SMM). Arrhenius plots for the chi(m)' peaks from 0.7-1.5 K gave the re-orientation energy barrier (DeltaE) of 10.5 K with a pre-exponential factor of 8.2x10(-8) s.     

Synthesis, reactivity, and properties of N-fused porphyrin rhenium(I) tricarbonyl complexes

The thermal reactions of N-fused tetraarylporphyrins or N-confused tetraarylporphyrins with Re2(CO)10 gave the rhenium(I) tricarbonyl complexes bearing N-fused porphyrinato ligands (4) in moderate to good yields. The rhenium complexes 4 are characterized by mass, IR, 1H, and 13C NMR spectroscopy, and the structures of tetraphenylporphynato complex 4a and its nitro derivative 15 are determined by X-ray single crystal analysis. The rhenium complexes 4 show excellent stability against heat, light, acids, bases, and oxidants. The aromatic substitution reactions of 4 proceed without a loss of the center metal to give the nitro (15), formyl (16), benzoyl (17), and cyano derivatives (19), regioselectively. In the electrochemical measurements for 4, one reversible oxidation wave and two reversible reduction waves are observed. Their redox potentials imply narrow HOMO-LUMO band gaps of 4 and are consistent with their electronic absorption spectra, in which the absorption edges exceed 1000 nm. Theoretical study reveals that the HOMO and LUMO of the rhenium complexes are exclusively composed of the N-fused porphyrin skeleton. Protonation of 4 takes place at the 21-position regioselectively, reflecting the high coefficient of the C21 atom in the HOMO orbital. The skeletal rearrangement reaction from N-confused porphyrin Re(I) complex (8) to N-fused porphyrin Re(I) complex (4) is suggested from the mechanistic study as well as DFT calculations.     

Whereabouts of missing atoms in a laser-injected Si: Part 1

In a stealth dicing of Si wafers, voids are formed in laser-induced modified volumes (LIMVs). Most of the voids are free from apparent defects such as dislocations and cracks. Needless to say, in what will become a void (pre-void) upon laser injection, Si atoms are present prior to the laser injection. The critical issue is where these missing atoms are after the laser injection. Two obvious possibilities are that (1) they remain inside the Si wafer as interstitials (I’s) or (2) these I’s reach the surface of the wafer to disappear. If (1) is the case, I’s are to coagulate to form dislocation loops of I-type upon post laser-injection annealing. However, it has been shown that this is not the case. In order to see whether (2) is the case, surfaces of a laser-injected Si wafer were studied by a scanning electron microscope in detail. No evidence of I’s having reached the surfaces was obtained.     

Organic thin films based on a dicyanovinyl-quaterthiophene: Influence of electrode configuration on third-order nonlinear optical properties measured by electroabsorption spectroscopy

Electroabsorption (EA) studies at room temperature on organic thin films based on a dicyanovinyl-quaterthiophene 4T-V(CN)₂ are reported. An electric field modulation is applied to the samples for two different electrode geometries, i.e. sandwich and coplanar versus the organic layer. Changes in optical absorption coefficient of 4T-V(CN)₂ based thin films are measured and analyzed to determine the character of the optical transition in the visible range (400-800 nm). Depending on the experimental electrode configuration, magnitude of electroabsorption responses are different, possibly due to different distribution of the externally applied electric field. The results indicate a higher resolution of EA response for the sandwich electrode configuration and confirm the charge transfer exciton character of 4T-V(CN)₂ in contrast to the unsubstituted quaterthiophene 4T. Finally, a third-order nonlinear susceptibility χ⁽³⁾ (−ω; ω, 0, 0) of 16 × 10⁻¹² e.s.u. is obtained.     

Manipulating Ge quantum dots on ultrathin SixGe1−x oxide films using scanning tunneling microscope tips

Germanium quantum dots (QDs) were extracted from ultrathin Si_xGe_1−x oxide films using scanning tunneling microscope (STM) tips. The extraction was most efficiently performed at a positive sample bias voltage of +5.0 V. The tunneling current dependence of the extraction efficiency was explained by the electric field evaporation transfer mechanism for positive Ge ions from QDs to STM tips. Ge QDs (∼7 nm) were formed and isolated spatially by extracting the surrounding Ge QDs with an ultrahigh density of >10¹² cm⁻². Scanning tunneling spectroscopy of the spatially-isolated QDs revealed that QDs with an ultrahigh density are electrically-isolated from the adjacent dots.     

Controlling anisotropy of GaSb(As)/GaAs quantum dots by self-assembled molecular beam epitaxy

A systematic study was performed to control the geometrical anisotropy of GaSb(As)/GaAs quantum dot structures formed by the Stranski–Krastanov growth mode of molecular beam epitaxy. In particular, effects of both the Sb₄ beam flux and the As₄ background pressure on the geometrical anisotropy were clarified and elongated QDs with lateral aspect ratio greater than 3 were successfully formed. Under a low As₄ background pressure, As₄ is found to act as surfactant to influence the adatom diffusion and change the density of QDs. By contrast, under high As₄ background pressure, the intermixing of As and Sb takes place and reduces strains induced by the lattice mismatch.     

Electric-field control of electron–hole wave functions in a wide quantum well

The electric field dependence of the electron/hole wave function and the radiation energy of an exciton in a Be-δ-doped 80 nm quantum well (QW) is studied experimentally and compared it with variational calculation. The photoluminescence (PL) spectra show Stark shifts depending on the gate electric field and PL intensity of the exciton of the first excited state has a dip in the electric-field dependence which reflects the node of the electron wave function.