Two organometallic fragments inclusioned in a 1,3-alternate calix[4]arene tetraphosphane: evidence for transition metal-arene interaction through the cavity

The preparation of an 1,3-alternate calix[4]arene tetraphosphane ligand, 25,26,27,28-tetrakis{2-(diphenylphosphino)ethoxy}calix[4]arene (4), is described. Ligand 4 is obtained in four steps in 17% overall yield. Reaction of 4 with AgBF4 produced the encapsulated two silver complex [Ag2{(P,P,P,P)-tetraphencalix[4]arene}](BF4)2. The solid-state structure shows that the encapsulated silver undergoes a substantial pi-interaction by two opposite arene rings. Rhodation of 4 employing [Rh(cot)2]BF4 yielded the encapsulated complex with a bent coordination mode. Two organometallic fragments inclusioned inside a 1,3-alternate calix[4]arene tetraphosphane was also achieved by the reaction of 4 with [PtH(PPh3)2 (thf)]+. Full characterization includes X-ray structural studies of compounds 4-6.     

A series of tetrahomodioxacalix[4]biscrown-n. Syntheses, crystal structures, and metal binding abilities

A series of novel tetrahomodioxacalix[4]biscrowns with crown-2, crown-3, crown-4, crown-5, and crown-6 units were synthesized. Conformations of each product are dependent on the base used and their conformation stabilities. All conformations were proven by NMR spectra and/or X-ray crystal structures. The 1,3-alternate homodioxacalix[4]biscrown-4 (4b) shows the best selectivity for K+, whereas the 1,3-alternate homodioxacalix[4]crown-5 (5) does for Cs+. Those selectivities are attributable to electrostatic interaction between the metal ion and the crown ring, as well as a pi-metal complexation. However, the C-1,2-alternate conformation does not take the metal ions regardless of the crown species as a result of steric hindrance from the methylene bridge of an ArCH2Ar unit.     

Correlated atomic force microscopy and fluorescence lifetime imaging of live bacterial cells

We report on imaging living bacterial cells by using a correlated tapping-mode atomic force microscopy (AFM) and confocal fluorescence lifetime imaging microscopy (FLIM). For optimal imaging of Gram-negative Shewanella oneidensis MR-1 cells, we explored different methods of bacterial sample preparation, such as spreading the cells on poly-L-lysine coated surfaces or agarose gel coated surfaces. We have found that the agarose gel containing 99% ammonium acetate buffer can provide sufficient local aqueous environment for single bacterial cells. Furthermore, the cell surface topography can be characterized by tapping-mode in-air AFM imaging for the single bacterial cells that are partially embedded. Using in-air rather than under-water AFM imaging of the living cells significantly enhanced the contrast and signal-to-noise ratio of the AFM images. Near-field AFM-tip-enhanced fluorescence lifetime imaging (AFM-FLIM) holds high promise on obtaining fluorescence images beyond optical diffraction limited spatial resolution. We have previously demonstrated near-field AFM-FLIM imaging of polymer beads beyond diffraction limited spatial resolution. Here, as the first step of applying AFM-FLIM on imaging bacterial living cells, we demonstrated a correlated and consecutive AFM topographic imaging, fluorescence intensity imaging, and FLIM imaging of living bacterial cells to characterize cell polarity.     

Improved Compatibility of Styrene-Maleic Anhydride Copolymer/Polyethylene Blends Through Reactive Mixing

Abstract

To improve the compatibility of styrene-maleic anhydride copolymer/low density polyethylene (SMA/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with SMA of which anhydride was converted to carboxylic acid (SMAAc). The infrared spectra of LDPE-g-HI established the presence of isocyanate group. In the blend morphology, some adhesions between the two phases and much finer dispersions were observed in the SMAAc/LDPE-g-HI blends, indicating that chemical reactions took place during the melt blending. The lower heat capacity change at the glass transition temperature demonstrated that chemical bonds were produced in the SMAAc/LDPE-g-HI blends. From the results of the rheological test, it was found that strong positive deviation from the mixing rule occurred in viscosity for the SMAAc/LDPE-g-HI blends, concerning with good adhesion and finer dispersions. In the measurement of tensile property, the improved mechanical properties for the SMAAc/LDPE-g-HI blends were shown.     

Critical Heat Flux for Downward Facing Boiling on a Coated Hemispherical Surface

An experimental study was performed to investigate the effect of surface coating on the critical heat flux for downward facing boiling on the outer surface of a hemispherical vessel. Steady-state boiling experiments were conducted in the subscale boundary layer boiling (SBLB) facility using test vessels with metallic microporous coatings to obtain the local boiling curves and the local critical heat flux (CHF) limits. Similar heat transfer performance was observed for microporous aluminum and microporous copper coatings. When compared to the corresponding data without coatings, the boiling curves for the coated vessels were found to shift upward and to the right. This meant that the CHF limit was higher with surface coating and that the minimum film boiling temperatures were located at higher wall superheats. In particular, the microporous coatings were found to enhance the local CHF values appreciably at all angular locations explored in the experiments. Results of the present study showed that the microporous aluminum coating was very durable. Even after many cycles of steady state boiling, the vessel coating remained rather intact, with no apparent changes in color or structure. Although similar heat transfer performance was observed for microporous copper coatings, the latter were found to be much less durable and tended to degrade after several cycles of boiling.     

Real Hypersurfaces in Complex Two-Plane Grassmannians with GTW Reeb Lie Derivative Structure Jacobi Operator

Mediterranean Journal of Mathematics - Using GTW connection, we considered a real hypersurface M in a complex two-plane Grassmannian $${G_{2}({\mathbb{C}}^{m+2})}$$ when the GTW Reeb Lie derivative...     

Composite of SiO2 and Hydrogel Having Microphase Separated Structure: Physical Properties Dependence on pH

Abstract

Organic-inorganic composite gel was prepared by using PEG-modified urethane acrylate (PMUA) gel and tetraethoxysilane (TEOS). PMUA gel was prepared by the phase-inversion emulsion polymerization of PMUA emulsion. The gelation of PMUA emulsion using this method enables PMUA gel to swell with H₂O, TEOS, and ethanol. Hydrolysis and condensation reaction rates of the sol-gel process are strongly influenced by the pH controlled by catalysts such as HCl and NH₄OH. Additionally, the morphology on the cross section of composite and the amount of silica ingredient incorporated into the composite gel were dependent on solvent, the molar ratio of H₂O to TEOS, as well as the pH value.

As the silica content increased, due to hydrogen bonds interacting between PMUA gel and SiO₂, particles, the tensile strength of composites considerably increased, whereas the elongation at break decreased. The incorporation of silica ingredient in PMUA gel/silica composites was verified with FTIR/ATR and SEM. The amount of the silica component in the composite was indirectly investigated by using TGA thermal analysis.