Oxygen Selectivity on Partially K Exchanged Na-A Type Zeolite at Low Temperature

In previous work by the authors on Na-A zeolite (Izumi et al., Japan Patent Toku-Kou-Shou 63-058614, 1988), it was shown that the combination of high-temperature calcination and operation of the adsorption step at low temperatures improved the selectivity for oxygen over nitrogen from air (Izumi et al., CATS J Meeting Abstracts, 31(2A), 10, 1989; Izumi and Suzuki, Adsorption, 6, 2000). Berlin discloses in his U.S. Patent 3282028 (1966) that the partial exchange of potassium ions for sodium ions in the Na-A type zeolite also improved selectivity for oxygen by reducing the uptake rate of nitrogen. It was therefore expected that the oxygen selectivity of Na-K-A with high-temperature calcination and low-temperature adsorption might be enhanced. For the confirmation of optimum conditions for the appearance of oxygen selectivity on Na-K-A, samples were prepared with a K exchange ratio varied from 0–20 mol% (0–2.4 K ions/unit cell), and a calcination temperature varied from 923 to 1073 K, and an experiment concerning oxygen and nitrogen adsorption on Na-K-A was undertaken with a small adsorbent column under pressure swing adsorption (PSA) conditions at adsorption temperatures from room temperature to 213 K. It was found that (a) the K exchange ratio of 7 mol% (0.84 K ions/unit cell), and (b) the calcination temperature of 993 K, resulted in a remarkable increase in oxygen selectivity. Under optimum conditions for Na-K-A, the oxygen separation factor was about 8. Na-K-A has the potential to effectively separate oxygen and nitrogen from air by means of PSA.     

Construction of Trinervitane and Kempane Skeletons Based on Biogenetical Routes

Based on the putative biogenesis of trinervitane‐ and kempane‐type diterpenes (Scheme 1), a biogenetic‐type transformation was simulated by cyclization of 7,16‐secotrinervita‐7,11,15‐triene‐2α,3α,17‐triol ( 23 ) and of its 17‐chloro derivative 30 . The requisite substrates were prepared from geranylgeranoic acid chloride 6 (Schemes 2, 4, and 5). Treatment of 30 with AgClO₄ at −20° provided the trinervitantrienediols 32 and 33 in 68 and 5% yields, while kempadienediol 35 was obtained in 50% yield by the same reagent at +20° (Scheme 7). The structures of the cyclization products were elaborated from detailed inspection of NMR spectra including H,H COSY, C,H COSY, and NOESY (Tables 1 and 2). The conformation of 30 and its plausible cyclization intermediate was discussed with the help of physical evidence, including X‐ray crystallographic analysis.     

Modification of interface structure and contact resistance between a carbon nanotube and a gold electrode by local melting

The electrical connection between a multiwalled carbon nanotube (MWNT) and a gold electrode on applying an electric current was studied by performing in situ transmission electron microscopy observations while simultaneous measuring the bias voltage and the electric current. The tip of the MWNT was brought into contact with the gold surface. When a current density of ∼10⁸ A/cm² flowed through the contact, the gold surface started to melt along the surface of the MWNT tip due to Joule heating. At about twice the current density, a drastic change was observed in the structure of the gold surface in the contact region. This structural change increased the contact area between the MWNT tip and gold, which reduced the electrical contact resistance.     

Rheo-Dielectric behavior of low molecular weight liquid crystals.

Dielectric relaxation behavior was examined for 4-4′-n-pentyl-cyanobiphenyl (5CB) and 4-4′-n-heptyl-cyanobiphenyl (7CB) under flow. In quiescent states at all temperatures examined, both 5CB and 7CB exhibited dispersions in their complex dielectric constant ε*(ω) at characteristic frequencies ω _c above 10⁶ rad s^–1. This dispersion reflected orientational fluctuation of individual 5CB and 7CB molecules having large dipoles parallel to their principal axis (in the direction of C≡N bond). In the isotropic state at high temperatures, these molecules exhibited no detectable changes of ε*(ω) under flow at shear rates . In contrast, in the nematic state at lower temperatures the terminal relaxation intensity of ε*(ω) as well as the static dielectric constant ε′(0) decreased under flow at . This rheo-dielectric change was discussed in relation to the flow effects on the nematic texture (director distribution) and anisotropy in motion of individual molecules with respect to the director. Received: 14 April 1998 Accepted: 29 July 1998     

Thin film characterization by total reflection x-ray fluorescence

Sensitive and accurate characterization of films thinner than a few nm used in nanoelectronics represents a challenge for many conventional production metrology tools. With capabilities in the 10¹⁰ at/cm², methods usually dedicated to contamination analysis appear promising, especially Total-reflection X-Ray Fluorescence (TXRF). This study shows that under usual configuration for contamination analysis, with incident angle smaller than the critical angle of the substrate, TXRF signal saturation occurs very rapidly for dense films (below 0.5 nm for HfO₂ films on Si wafers using a 9.67 keV excitation at 0.5°). Increasing the incident angle, the range of linear results can be extended, but on the other hand, the TXRF sensitivity is degraded because of a strong increase of the measurement dead time. On HfO₂ films grown on Si wafers, an incident angle of 0.32° corresponding to a dead time of 95% was used to achieve linear analysis up to 2 nm. Composition analysis by TXRF, and especially the detection of minor elements into thin films, requires the use of a specific incident angle to optimize sensitivity. Although quantitative analyses might require specific calibration, this work shows on Co–based films that the ratio between minor elements (W, P, Mo) and Co taking into account their relative sensitivity factors is a good direct reading of the composition.     

Evidence for a weakening ‘dead zone’ in Tokyo Bay over the past 30?years

Weakened hypoxia in the past 30?years at a dredged area in Tokyo Bay was proven by the existence of amorphous hematite (α-Fe2O3) in sediments. The chemical states of iron in sediments can become a proxy for the scale of anoxia at the time of sedimentation. In 2009, we collected core sediments from a dredged area off Makuhari in Tokyo Bay that is very strongly anoxic in the summer. Every layer of the sediments was analysed by ⁵⁷Fe M?ssbauer spectroscopy and excess 210Pb dating, and amorphous hematite was identified in the sediments from the 1976–1979, 1986–1989 and 2006–2009 layers. Using an estimate based on the Eh-pH diagram optimized for the sedimental environment, the existence of hematite in the dredged area proves that the scale of hypoxia/anoxia is decreasing, and these results agree well with the observed dissolved oxygen level of the seawater mass.     

Effects of Surface Oxygen of Activated Carbon on Alkaloid Adsorption: A Molecular Dynamics Simulation Study

The influence of the density and the type of surface oxygen on the adsorption of berberine alkaloid onto activated carbon was investigated using the molecular dynamics simulation method in vacuum. The carbon surface consisted of a basal plane of graphite and surface oxygen groups which were bonded on the graphite plane in a regular square array with various densities. Two types of surface oxygen groups, =O and —OH, were employed. The simulation results showed that the berberine alkaloids were favorable to be adsorbed on the negative charged carbon surfaces. It was indicated that the vdw attraction of the carbon surface to the alkaloid molecule dominates the adsorption only at the lower surface density of oxygen. It is also indicated that a good adsorptive selectivity for a certain berberine alkaloid can be obtained by controlling the density of surface oxygen.The adsorption simulation of berberine alkaloids onto activated carbon in the presence of water was also carried out by using a dome-shape molecular model for presenting the alkaloid/water/carbon system. It was found that the adsorption of berberine alkaloids on the activated carbon which has a higher density of surface oxygen was strongly inhibited by the presence of water.     

Membrane Emulsification Using Sol-Gel Derived Macroporous Silica Glass

A macroporous silica glass membrane with continuous cylindrical pores was prepared by a sol-gel process using phase separation. The applicability of the sol-gel derived macroporous silica to the membrane emulsification process was evaluated in comparison with a conventional SPG (Silasu Porous Glass) membrane.Aqueous colloidal silica in one side of the membrane was emulsified through the pores under an applied pressure to a toluene bath containing surfactant. With the sol-gel and SPG membranes with respective median pore diameters of 0.6 and 1.0 m, emulsions with almost the same droplet size centered around 3 m were obtained. The permeation rate of the sol-gel derived membrane was about 1.6 times faster than SPG, which reflected higher pore volume of the former one.     

FEMTOSECOND STUDIES OF PRIMARY PHOTOPROCESSES IN OCTOPUS RHODOPSIN

Abstract— Femtosecond spectroscopy of octopus rhodopsin in H₂O and D₂O was performed over a very wide spectral region of 400–1000 nm. Transient gain and absorption from the excited state were observed for the first time around 650 and 700 nm, respectively, just after 300 fs pulse excitation. Bathorhodopsin was formed within 400 fs from the excited state; therefore, the cis-trans isomerization completes within 400 fs. The first intermediate "primerhodopsin" found in our previous paper is most likely "quasi-thermal" bathorhodopsin, in which the local thermalization of the chromophore is achieved. Then cooling down of the chromophore to the surrounding protein temperature takes place with 20 ± 10 ps along with blue-shifting of a spectrum of 10 ± 5 nm. In addition to these observations, a prominent gain in the region of > 850 nm was observed and decayed with 2–3 ps in H₂O. A similar time constant was estimated for a partial decay of an induced absorption around 600 nm. This process may be related with two forms of bathorhodopsin reported previously. In this scheme, two forms of bathorhodopsin are formed with time constants of about 400 fs and 2 ps. In the sample in D₂O, time constant of 3–4 ps was obtained for the slower process.