Effects of Modified MMT on Mechanical Properties of EVA/MMT Nanocomposites and Their Foams

In this study, nanocomposites of poly(ethylene-co-vinyl acetate) with two kinds of organically modified montmorillonite (OMMT) were prepared by melt intercalation. Their structures and mechanical properties were characterized by X-ray diffraction (XRD) and tensile test respectively. Especially, foaming of these nanocomposites mixed with chemical blowing agent was carried out through compression molding. Influences of OMMT on foaming ratio and mechanical properties were investigated by density test, tensile test and tear test. Results revealed that both kinds of OMMT with proper content increased tensile strength and Young's modulus of nanocomposites without a compromise of elongation at break. For foaming, OMMTs apparently improved foaming ratio and in particular, one of them can improve tear strength, tensile strength, Young's modulus and elongation although the density was decreased.     

Highly phosphorescent iridium complexes with chromophoric 2-(2-hydroxyphenyl)oxazole-based ancillary ligands: interligand energy-harvesting phosphorescence

We disclose a controlled phosphorescence color tuning in a series of cyclometalated heteroleptic IrIII complexes (IrIII bis(2-(2,4-difluorophenyl)pyridinato- C,N (2'))(LX)) containing chromophoric 2-(2-hydroxyphenyl)oxazole-derivative ancillary ligands (LX). From a cyclometalated chloride-bridged IrIII dimer, three highly emissive cyclometalated heteroleptic IrIII complexes were obtained in good yields, each with a different conjugative plane in the chromophoric ancillary ligand (i.e., 2-(2-hydroxyphenyl)-4-methyloxazole, 2-(2-hydroxyphenyl)-6-methylbenzoxazole, and 2-(2-hydroxyphenyl)naphthoxazole). The three IrIII complexes showed highly efficient greenish blue (500 nm), green (525 nm), and yellow (552 nm) phosphorescence, respectively; a regular ca. 0.11 eV bathochromic shift was observed for each additional phenyl ring fused to the oxazole ring in the ancillary ligand. From the absorption, electrochemical measurements, static and transient photoluminescence (PL), and time-dependent density functional theory (TD-DFT) calculations, it can be concluded that the IrIII complexes have a single emission center with dual excitation paths. Finally, this characteristic energy-harvesting phosphorescence was further demonstrated in electrophosphorescence devices.     

Structural change of 1-butyl-3-methylimidazolium tetrafluoroborate + water mixtures studied by infrared vibrational spectroscopy

Mixtures of ionic liquid (IL, 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4]) and water with varying concentrations were studied by attenuated total reflection infrared absorption and Raman spectroscopy. Changes in the peak intensities and peak positions of CHx (x = 1, 2, 3) vibration modes of the cation of the IL and OH vibration modes of the water molecules were investigated. Peaks from normal-mode stretch vibrations of CH bonds belonging to the imidazolium ring of the cation did not change their positions, while those from the terminal methyl group of the butyl chain blueshifted by approximately 10 cm-1 with the addition of water. On the other hand, change in the spectral shape in the OH stretch vibration region shows hydrogen-bonding network of water molecules breaking down rapidly as the IL is added. Trends in the change of the peak positions and the peak intensities suggested qualitative change of the intermolecular structure in the [BMIM][BF4] + H2O mixture at 32 +/- 2 and 45 +/- 2 mol/L of water concentration.     

Transcriptional targeting of gene expression in breast cancer by the promoters of protein regulator of cytokinesis 1 and ribonuclease reductase 2

For cancer gene therapy, cancer-specific over- expression of a therapeutic gene is required to reduce side effects derived from expression of the gene in normal cells. To develop such an expression vector, we searched for genes over-expressed and/or specifically expressed in cancer cells using bioinformatics and have selected genes coding for protein regulator of cytokinesis 1 (PRC1) and ribonuclease reductase 2 (RRM2) as candidates. Their cancer-specific expressions were confirmed in both breast cancer cell lines and patient tissues. We compared each promoter's cancer-specific activity in the breast normal and cancer cell lines using the luciferase gene as a reporter and confirmed cancer-specific expression of both PRC1 and RRM2 promoters. To test activities of these promoters in viral vectors, the promoters were also cloned into an adeno-associated viral (AAV) vector containing green fluorescence protein (GFP) as the reporter. The GFP expression levels by these promoters were various depending on cell lines tested and, in MDA-MB-231 cells, GFP activities derived from the PRC1 and RRM2 promoters were as strong as that from the cytomegalovirus (CMV) promoter. Our result showed that a vector containing the PRC1 or RRM2 promoter could be used for breast cancer specific overexpression in gene therapy.     

5- And 6-exocyclic products, cis-2,3,5-trisubstituted tetrahydrofurans, and cis-2,3,6-trisubstituted tetrahydropyrans via Prins-type cyclization

Exocyclic products having cis-2,5 and cis-2,6 substitution were synthesized from terminally substituted alkynyl alcohols with various aldehydes via Prins-type cyclization in good yields. It is of interest that synthesized 5- and 6-exocyclic vinyl cations generated as a result of Prins-type cyclization could be trapped as a vinyl triflate in CH2Cl2 to give 3-furanylidenes and 3-pyranylidenes. Those 3-furanylidenes and 3-pyranylidenes underwent hydrolysis to give the corresponding 3-acyl-substituted products having all-cis-configured isomers, such as 2,3,5-trisubstituted tetrahydrofurans and 2,3,6-trisubstituted tetrahydropyrans.     

Hierarchical Self‐Assembly of Poly‐Pseudorotaxanes into Artificial Microtubules

Hierarchical self‐assembly of building blocks over multiple length scales is ubiquitous in living organisms. Microtubules are one of the principal cellular components formed by hierarchical self‐assembly of nanometer‐sized tubulin heterodimers into protofilaments, which then associate to form micron‐length‐scale, multi‐stranded tubes. This peculiar biological process is now mimicked with a fully synthetic molecule, which forms a 1:1 host‐guest complex with cucurbit[7]uril as a globular building block, and then polymerizes into linear poly‐pseudorotaxanes that associate laterally with each other in a self‐shape‐complementary manner to form a tubular structure with a length over tens of micrometers. Molecular dynamic simulations suggest that the tubular assembly consists of eight poly‐pseudorotaxanes that wind together to form a 4.5 nm wide multi‐stranded tubule.     

γ‐Glutamylcysteine‐ and Cysteinylglycine‐Directed Growth of Chiral Gold Nanoparticles and their Crystallographic Analysis

Chiral optical metamaterials with delicate structures are in high demand in various fields because of their strong light–matter interactions. Recently, a scalable strategy for the synthesis of chiral plasmonic nanoparticles (NPs) using amino acids and peptides has been reported. Reported herein, 3D chiral gold NPs were synthesized using dipeptide γ‐Glu‐Cys and Cys‐Gly and analyzed crystallographically. The γ‐Glu‐Cys‐directed NPs present a cube‐like outline with a protruding chiral wing. In comparison, the NPs synthesized with Cys‐Gly exhibited a rhombic dodecahedron‐like outline with curved edges and elliptical cavities on each face. Morphology analysis of intermediates indicated that γ‐Glu‐Cys generated an intermediate concave hexoctahedron morphology, while Cys‐Gly formed a concave rhombic dodecahedron. NPs synthesized with Cys‐Gly are named 432 helicoid V because of their unique morphology and growth pathway.     

Two-photon fluorescent turn-on probe for lipid rafts in live cell and tissue

We report a new two-photon fluorescence turn-on probe 6-[(E)-3-oxo-1-dodecenyl]-2-[N-methyl-N-(carboxymethyl)amino]naphthalene (CL2) that is designed specifically for visualizing lipid rafts in living cells and tissues. This probe emits much brighter two-photon excited fluorescence in lipid rafts than in non-raft domains and allows direct visualization of the lipid rafts in the live cells and pyramidal neuron layer of the CA1 region at a depth of 100-250 mum in live tissues using two-photon microscopy.