Nb/Au/(1 1 0)YBa2Cu3O7−δ Josephson junctions: evidence against atomic scaled “corner junctions”

We report on I–V characteristics for in situ formed Nb/Au/(1 1 0)YBa₂Cu₃O_7−δ (YBCO) Josephson junction, where the homoepitaxial (1 1 0)YBCO film shows ultra-smooth surface morphology. The field dependence of critical supercurrent I_c shows anisotropic large junction behavior with normal Fraunhofer patterns expected from BCS model of d_x²−y² wave superconductors. This strongly suggests that the Nb/Au/(1 1 0)YBCO junctions cannot be regarded as atomic scaled corner junctions, in contrast with (0 0 1)/(1 1 0)YBCO grain boundary junctions to show “π-junction” with a pronounced dip near zero fields in field modulation of I_c.     

Improvement of an Automated Sample Injection System for Pillar Array Columns to Increase Analytical Reproducibility

In our previous study, we developed an automatic sample injection system for pillar array columns for quantitative analysis. An autosampler was used to maintain a constant sample injection volume. However, the sample was diluted during injection using the autosampler, thus deteriorating the analytical reproducibility. In this study, we have substituted the autosampler with a syringe pump to overcome the abovementioned problem and improve the system. Sample dilution was avoided by filling the entire capillary with the sample at a constant rate. This improved system also increased the analytical reproducibility. In the previous system, the relative standard deviation (RSD) exceeded 17% of the peak height for coumarin dyes. In contrast, the improved system decreased the RSD to the range 1.2–1.8%. The analytical reproducibility was evaluated by using five types of amino acids. The RSD of each peak height was within 3.0%, confirming good reproducibility. These results indicate that the sample injection method developed in this study can be applied to biological sample analyses as a simple quantitative analysis method for pillar array columns.     

DNA Damage and Apoptosis Induced by Photosensitization of 5,10,15,20-Tetrakis (N-methyl-4-pyridyl)-21H,23H-porphyrin via Singlet Oxygen Generation

Cancer photodynamic therapy (PDT) requires photosensitizers that efficiently and selectively destroy tumor cells. We investigated 5,10,15,20-tetrakis ( N -methyl-4-pyridyl)-21 H ,23 H -porphyrin (TMPyP) as a potential cancer treatment. Confocal fluorescence microscopy showed that TMPyP was localized in the nuclei, whereas 5-aminolevulinic acid (ALA)-derived protoporphyrin IX (PPIX) was localized diffusely in the cytoplasm of human leukemia (HL-60) cells. In HL-60 cells under UVA irradiation, TMPyP effectively induced apoptosis. Moreover, 8-oxo-7,8-dihydro-2'-deoxyguanosine, an oxidative product of 2'-deoxyguanosine, was accumulated in the DNA of cells treated with photoirradiated TMPyP, whereas only small amounts were observed in ALA-treated cells in the presence of UVA light. TMPyP and UVA caused extensive damage at every guanine residue in DNA fragments obtained from the human p 53 tumor suppressor gene and the c-Ha- ras -1 proto-oncogene, whereas PPIX induced little DNA damage under these conditions. Electron spin resonance spectroscopy using a singlet oxygen (¹O₂) probe and D₂O showed that photoexcited TMPyP generated ¹O₂. These results suggest that photoexcited TMPyP reacts with oxygen to generate ¹O₂, which in turn, oxidizes guanine residues. Taken together, the results demonstrated that TMPyP was localized in the nucleus where it was photosensitized to induce DNA damage, suggesting that TMPyP may have clinical utility as a nucleus-targeted PDT.     

Oligomeric polymer surfactant driven self-assembly of phenylene-bridged mesoporous materials and their physicochemical properties

The detailed synthesis of highly hydrophobic average pore benzene-bridged hybrid mesoporous silicas under an acidic medium is described. With the use of a 1,4-bis(triethoxysilane)benzene silsesquioxane precursor and biodegradable alkyl polyoxyethylene (Brij-56 or Brij-76) nonionic surfactant oligomers as supramolecular templates, no molecular scale periodicity was observed. The well-defined mesoporous materials could be synthesized with two-dimensional hexagonal (p6mm) symmetries. The textural and surface properties (adsorption isotherms of water and benzene vapors) were estimated and were compared to the analogous benzene-bridged mesoporous silica with molecular scale periodicity which was prepared using cationic surfactant under basic conditions. Different textural properties resulted for the two kinds of materials and revealed some important insights regarding the structure and nature of the materials.     

Quantum effects on capacitively coupled intrinsic Josephson junctions

We numerically study quantum effects in intrinsic Josephson junctions of layered high-T_c superconductors in order to explain recent experimental observations on the switching rate enhancement in the low temperature quantum regime. We pay attention to the capacitive coupling between neighboring junctions and perform simulations for the Schrödinger equation derived from the Hamiltonian describing the capacitive coupling. The simulation results reveal that the phase dynamics show synchronous behaviors when entering the quantum regime. This is qualitatively consistent with the experimental result.     

Infrared spectroscopic investigation of poly(2-methoxyethyl vinyl ether) during thermosensitive phase separation in water

Hydration changes of poly(2-methoxyethyl vinyl ether) (PMOVE) synthesized via living cationic polymerization have been investigated during a temperature-responsive phase separation in water by using infrared spectroscopy. An aqueous PMOVE solution has lower critical solution temperatures (LCSTs) of 66 degrees C in H2O and 65 degrees C in D2O at approximately 15 wt %. During phase separation, the C-H stretching (nu(C-H)) bands of PMOVE shift downward (red shift). In particular, the IR band assigned to the antisymmetric stretching vibration of the terminal methyl groups exhibits a remarkably large red shift by 16 cm-1. The band also exhibits a red shift with increasing polymer concentration at T < Tp. Density functional theory (DFT) calculations of the models of hydrated PMOVE indicate that the shift is due mainly to the breaking of hydrogen bonds (H-bonds) between the oxygen of the methoxy groups and water and partially to the breaking of the CH...O H-bond to them.     

Photoluminescence from single silicon quantum dots excited via surface plasmon polaritons

Single dot spectroscopy of Si quantum dots (QDs) was performed by using surface plasmon polariton (SPP)-mediated excitation in the attenuated total reflection geometry with a MgF₂/Ag film on the base of a prism. Thanks to the 16 times enhancement of the incident electric field and very small background signal, PL from single Si QDs was observed clearly. This proves the usefulness of the technique for the detection of inherently weak emission of Si QDs.     

Periodic Mesoporous Organosilica with Molecular‐Scale Ordering Self‐Assembled by Hydrogen Bonds

Nanoporous materials with functional frameworks have attracted attention because of their potential for various applications. Silica‐based mesoporous materials generally consist of amorphous frameworks, whereas a molecular‐scale lamellar ordering within the pore wall has been found for periodic mesoporous organosilicas (PMOs) prepared from bridged organosilane precursors. Formation of a “crystal‐like” framework has been expected to significantly change the physical and chemical properties of PMOs. However, until now, there has been no report on other crystal‐like arrangements. Here, we report a new molecular‐scale ordering induced for a PMO. Our strategy is to form pore walls from precursors exhibiting directional H‐bonding interaction. We demonstrate that the H‐bonded organosilica columns are hexagonally packed within the pore walls. We also show that the H‐bonded pore walls can stably accommodate H‐bonding guest molecules, which represents a new method of modifying the PMO framework.