Protonic Conduction and O-H Bonding State in Phosphate Glasses

Abstract

Protons in alkaline-earth phosphate glasses give much higher mobility than those in silicate glasses. This is caused by the difference in O-H bonding state. Protons in P-OH form a strong hydrogen bonding with oxygen anion, resulting in formation of weak O-H bond.

The electrical conductivity of the glasses is proportional to the square of the proton concentration. The activation energy for the conduction is related to ν_OH, peak wavenumber of infrared absorption band (around～3000 cm^?1), due to fundamental O-H stretching vibration. The mobility of protons increases with decreasing ν_OH, which depends on the species of ions included in the phosphate glasses.     

Molecular interactions between lipid bilayers and a water-soluble polymer

Molecular interactions between lipid bilayers (liposomes) and chondroitin sulfate C (CS), a water soluble polymer, have been investigated in terms of zeta-potential, particle size, microscopic-viscosity, microscopic-polarity of liposomes and permeability of calcein. Microscopic morphology is dramatically changed by the addition of CS to the positively charged liposomes (Pos.L), while it is not changed by the addition to uncharged liposomes (Unc.L) or negatively charged liposomes (Neg.L). The absolute value of the particle size of Pos.L increases with the addition of CS, while the zeta- potential of Pos.L decreases. Permeability of Pos.L decreases with an increase in the concentration of CS. Phase transition temperature of Pos.L is changed after the addition of CS. These values, however, are not changed for the other liposomes by the addition of CS. The results of gel filtration chromatography show that CS is absorbed on the Pos.L surface. Microscopic viscosity is also increased by the addition of CS to Pos.L due to the adsorption of CS.     

Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C60 to Afford Efficient Photodriven Charge Separation

Inclusion complexes of benzo‐ and dithiabenzo‐crown ether functionalized monopyrrolotetrathiafulvalene (MPTTF) molecules were formed with Li⁺@C₆₀ ( 1? Li⁺@C₆₀ and 2? Li⁺@C₆₀). The strong complexation has been quantified by high binding constants that exceed 10⁶ M ^?1 obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6‐311G(d,p) level, the orbital interactions between the crown ether moieties and the π surface of the fullerene together with the endohedral Li⁺ have a crucial role in robust complex formation. Interestingly, complexation of Li⁺@C₆₀ with crown ethers accelerates the intersystem crossing upon photoexcitation of the complex, thereby yielding ³(Li⁺@C₆₀)*, when no charge separation by means of ¹Li⁺@C₆₀* occurs. Photoinduced charge separation by means of ³Li⁺@C₆₀* with lifetimes of 135 and 120 μs for 1? Li⁺@C₆₀ and 2? Li⁺@C₆₀, respectively, and quantum yields of 0.82 in PhCN have been observed by utilizing time‐resolved transient absorption spectroscopy and then confirmed by electron paramagnetic resonance measurements at 4 K. The difference in crown ether structures affects the binding constant and the rates of photoinduced electron‐transfer events in the corresponding complex.     

Highly efficient cryogenically-cooled Yb:YAG laser

A MOPA laser system for high pulse energy and high average power has been developed by using a cryogenic Yb:YAG. In the regenerative amplifier with our original TRAM architecture, the high pulse energies of 6.5 and 1.5 mJ were obtained at the repetition rate of 200 Hz and 1 kHz, respectively. An optical efficiency was as high as η_o-o = 9.3% with an excellent beam quality of M ² < 1.1, which ensured that a cryogenic Yb:YAG TRAM had a high thermal strength. The following four pass power amplifier with a cryogenic Yb:YAG rod showed 140 mJ at 100 Hz. Both a high optical efficiency of η_o-o = 30% and a high slope efficiency of η_s = 44% showed that an efficient laser operation could be realized for a power amplification with both a high pulse energy and a high average power by using a cryogenic Yb:YAG.     

Synthesis of new photoresponsive polyesters containing norbornadiene moieties by the ring‐opening copolymerization of donor–acceptor norbornadiene dicarboxylic acid anhydride with donor–acceptor norbornadiene dicarboxylic acid monoglycidyl ester derivatives

The ring‐opening copolymerization of donor–acceptor norbornadiene (D–A NBD) dicarboxylic acid monoglycidyl ester derivatives with D–A NBD dicarboxylic acid anhydride was performed with tetraphenylphosphonium bromide as a catalyst in toluene to produce new norbornadiene (NBD) polyesters containing D–A NBD moieties in the main chain and in the side chain in one step in good yields. The photoisomerization of the D–A NBD moieties in these polyesters proceeded very smoothly to give the corresponding quadricyclane groups. Because these NBD polyesters contained many NBD moieties in the polymer chain, they had the highest capacity for heat storage in the D–A NBD polymers reported so far. The stored thermal energy of the irradiated polyesters was evaluated by differential scanning calorimetry analysis to be approximately 150–190 J/g. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4412–4421, 2005     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

Enzymatic silicone oligomerization catalyzed by a lipid-coated lipase

A lipid (1)-coated lipase can catalyze the oligomerization of diethoxydimethylsilane (DEDMS) in isooctane containing 2wt% water, where the polymerization occurs at the OH group of the coating lipid (1) in the enzyme cavity.     

Multiple reflections of Lamb waves at a delamination

Wave propagation in laminated plates with delaminations was calculated using the semi-analytical finite element method. The visualization results and deeper numerical analyses revealed the following phenomena on the fundamental Lamb modes at delamination regions of laminated plates. First, Lamb wave propagates toward the delamination, and then splits into two independent waves at the "Entrance" of the delamination with no significant reflections. These two waves reach the "Exit" of the delamination with the different phases and arrival time. Thus reflected and transmitted waves are excited at the Exit. The repetition of such reflections at the Exit causes the multiple reflections at regular intervals corresponding to the delamination size.     

Flow characteristics of pressure reducing valve with radial slit structure for low noise

Pressure reducing valves are widely used to maintain the pressure of gas reservoirs to specific values. In a normal valve, supply pressure is decompressed with an orifice structure. When compressed air passes through the orifice structure, considerable noise occurs at the downstream side. In this paper, we have developed a radial slit structure that can reduce pressure without noise. The noise is reduced by changing the orifice structure into the radial slit structure. The radial slit structure valve reduces pressure without noise by suppressing the generation of turbulence and shock wave at the downstream. The analysis of the flow in radial slit structure was achieved by CFD2000 software. The flow rate and pressure distribution were simulated and compared with the experimental result. To confirm the generation of shock wave, the flow of orifice and radial slit structure at the downstream was visualized by Schlieren photography method. A shock wave was generated in the orifice structure, but no shock wave was generated in the radial slit structure. Noise reduction efficiency was investigated by the experiment. The experiment apparatus was set up to JIS standards. The experimental results indicated that the noise level decreased by approximately 40 dB in the slit structure. It is confirmed that the radial slit structure has effectiveness for low noise in the pressure reducing flow. And, it is expected that it can be applied to various kinds of industrial fields.