Electronic effect of η5-cyclopentadienyl and η3-allyl ligands on the nature of the metal—olefin bond: Reversal of the relative olefin affinity of palladium(II) and platinum(II) ions

The barrier to olefin rotation in [Pt(η³-CH₂CMeCH₂)(olefin)(PPh₃)]PF₆ (3) (olefin = CH₂CH₂, E-MeCHCHMe) has been found to be extremely low compared to those in the other known, 4-coordinate olefin complexes of Pt^II. This can be ascribed to the smaller steric congestion around the olefin in 3. The corresponding barrier in [Pt(η⁵-C₅H₅)(CH₂CH₂)(PPh₃]ClO₄ (2), possessing likewise small steric congestion, was substantially higher than that in 3 (olefin = CH₂CH₂). The ¹³C and ³¹P NMR measurements have revealed much larger J(Pt-C(olefin)) in 2 than that in 3 (olefin = CH₂CH₂), while J(Pt-P) are comparable in these two. Stability constant data suggested that Pd^II ion in the Pd(η⁵-C₅H₅)(PPh₃)⁺ moiety is a better π-donor to olefins than Pt^II ion in the Pt(η³-CH₂CMeCH₂)(PPh₃)⁺ moiety, a reversal of the normal trend in the relative olefin affinity of these metal ions. The above spectral and stability features have been related to the electronic effect of the Cp ligand in enhancing the π back-bond interaction in one particular orientation of the CC bond.     

Electrophoretic analysis of the cleaved form of serpin,squamous cell carcinoma antigen-1 in normal and malignant squamous epithelial tissues

The aim of this study was to detect the cleaved form of serine proteinase inhibitor (serpin), squamous cell carcinoma (SCC) antigen-1 in normal and malignant squamous epithelial tissues, which implies the presence of its target proteinase. The cleaved SCC antigen-1 in normal squamous epithelium was identified as a single spot with pI 6.35 and M(r) 40,000 by two-dimensional electrophoresis (2-DE) combined with immunoblotting. Interestingly, the cleaved form showed different biochemical properties in heat stability or immunoreactivity with a monoclonal antibody for SCC antigen (Mab 426) compared to intact SCC antigen-1. Furthermore, sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analysis of tissue extracts showed an abundant 40 kDa band of cleaved SCC antigen-1 in tumor tissue compared to normal tissue. Among the potential target proteinase of SCC antigen-1, immunoblotting analyses revealed that cathepsin L2 was remarkably overexpressed in tumor tissue, while cathepsin L was expressed in both normal and tumor tissues. These findings indicate that SCC antigen-1 interacts with specific endogenous proteinases such as cathepsins L and L2 in physiological and pathological states of squamous epithelium.     

Spatial frequency selective reconstruction using Fourier transform holograms generated in functionalized mesogenic composites

We have demonstrated spatial frequency selective reconstruction (SFSR) of two-dimensional optical images by using functionalized mesogenic composites possessing real-time holographic capability. The two-dimensional optical image was Fourier transformed by a lens and part of the spatial frequency was brought into interference with the reference beam in the Raman-Nath regime. The SFSR images were observed in the self-diffraction patterns and we calculated the expected reconstructed images which were in good agreement with the observed images.     

Mouse bone marrow‐derived mesenchymal stem cell response to nanostructured titanium substrates produced by high‐pressure torsion

Mesenchymal stem cells (MSCs) with the ability to differentiate into various mesoderm‐like cells are known to migrate to various organs to repair injured tissues. They can attach to the implant surface, differentiate into bone‐forming cells, and ultimately osseointegrate with the prosthesis. This study investigates bone marrow‐derived mesenchymal stem cellular response to the grain structure of titanium substrates produced by high‐pressure torsion and annealing processes. Cell attachment, proliferation, viability, and morphology are evaluated on the surface of differently processed nanostructured and coarse‐grained samples. The bacterial adhesion and calcium phosphate crystal formation and growth are also assessed on the surface of the substrates. The nanostructured titanium shows significantly higher cell adhesion, proliferation, spreading, and viability compared with the untreated and coarse‐grained titanium substrates. The adhesion of bacteria is lower and surface bioactivity is higher on the surface of the nanostructured titanium substrate. The results demonstrate the superior MSC compatibility, antibacterial efficacy, and surface bioactivity of the nanostructured titanium substrates, which could lead to early implant fixation and improved osseointegration. Copyright © 2012 John Wiley & Sons, Ltd.     

Design, construction, and characterization of high-performance membrane fusion devices with target-selectivity

Membrane fusion proteins such as the hemagglutinin glycoprotein have target recognition and fusion accelerative domains, where some synergistically working elements are essential for target-selective and highly effective native membrane fusion systems. In this work, novel membrane fusion devices bearing such domains were designed and constructed. We selected a phenylboronic acid derivative as a recognition domain for a sugar-like target and a transmembrane-peptide (Leu-Ala sequence) domain interacting with the target membrane, forming a stable hydrophobic α-helix and accelerating the fusion process. Artificial membrane fusion behavior between the synthetic devices in which pilot and target liposomes were incorporated was characterized by lipid-mixing and inner-leaflet lipid-mixing assays. Consequently, the devices bearing both the recognition and transmembrane domains brought about a remarkable increase in the initial rate for the membrane fusion compared with the devices containing the recognition domain alone. In addition, a weakly acidic pH-responsive device was also constructed by replacing three Leu residues in the transmembrane-peptide domain by Glu residues. The presence of Glu residues made the acidic pH-dependent hydrophobic α-helix formation possible as expected. The target-selective liposome-liposome fusion was accelerated in a weakly acidic pH range when the Glu-substituted device was incorporated in pilot liposomes. The use of this pH-responsive device seems to be a potential strategy for novel applications in a liposome-based delivery system.     

Nanoscale coupling of photons to vibrational excitation of Ag nanoparticle 2D array studied by scanning tunneling microscope light emission spectroscopy

Scanning tunneling microscope light emission (STM-LE) spectroscopy has been utilized to elucidate the luminescence phenomena of Ag nanoparticles capped with myristate (myristate-capped AgNP) and 2-methyl-1-propanethiolate (C(4)S-capped AgNP) on the dodecanethiol-precovered Au substrate. The STM imaging revealed that myristate-capped AgNPs form an ordered hexagonal array whereas C(4)S-capped AgNPs show imperfect ordering, indicating that a shorter alkyl chain of C(4)S-capped AgNP is not sufficient to form rigid interdigitation. It should be noted that such a nanoparticle ordering affects the luminescence properties of the Ag nanoparticle. We found that the STM-LE is only detected from the Ag nanoparticles forming the two-dimensional superlattice. This indicates that the STM-LE of the Ag nanoparticle is radiated via the collective excitation of the local surface plasmon resonance (LSPR) spread over the Ag nanoparticles. Note that the STM-LE spectra of the Ag nanoparticles exhibit spike-like peaks superimposed on the broad light emission peak. Using Raman spectroscopy, we concluded that the spike-like structure appearing in the STM-LE spectra is associated with the vibrational excitation of the molecule embedded between Ag nanoparticles.     

Effects of recording wavelength on three-dimensional vector holograms in photoreactive liquid crystal composites

Effects of recording wavelength on the recently proposed (Sasaki, 2008) three-dimensional vector holograms, in which the optical anisotropy is three-dimensionally modulated, are presented experimentally and theoretically. The polarization states of the interference light are three-dimensionally modulated due to both the polarization interference and optical anisotropy in the recording medium. These spatial distributions of the polarization states and the resulting diffraction properties in the three-dimensional vector holograms are strongly dependent on the recording wavelength. Theoretical consideration based on the finite-difference time-domain (FDTD) method reveals the mechanism of the optical characteristics of the three-dimensional vector holograms recorded by various kinds of light sources with different wavelengths.     

Instrumental neutron activation analysis of an enriched 28Si single-crystal

The determination of the Avogadro constant plays a key role in the redefinition of the kilogram in terms of a fundamental constant. The present experiment makes use of a silicon single-crystal highly enriched in ²⁸Si that must have a total impurity mass fraction smaller than a few parts in 10⁹. To verify this requirement, we previously developed a relative analytical method based on neutron activation for the elemental characterization of a sample of the precursor natural silicon crystal WASO 04. The method is now extended to fifty-nine elements and applied to a monoisotopic ²⁸Si single-crystal that was grown to test the achievable enrichment. Since this crystal was likely contaminated, this measurement tested also the detection capabilities of the analysis. The results quantified contaminations by Ge, Ga, As, Tm, Lu, Ta, W and Ir and, for a number of the detectable elements, demonstrated that we can already reach the targeted 1 ng/g detection limit.