Clathrate-hydrate film growth along water/hydrate-former phase boundaries—numerical heat-transfer study

This paper describes two analytic models for the heat-transfer-controlled lateral growth of a clathrate-hydrate film along a planar interface between liquid water and an immiscible hydrate-forming fluid (or guest fluid), such as methane or carbon dioxide. The two models are different from each other only regarding the assumption of the film-front geometry. Either model assumes the film to be uniform and constant in thickness, ignoring possible changes in the thickness on a time scale relevant to its lateral growth. Another fundamental assumption employed in the model is that the film's hydrate-forming front is maintained at the hydrate/guest/water three-phase equilibrium temperature, thereby forming a two-dimensional temperature distribution in the surrounding three-phase space. Based on these assumptions, the transient, two-dimensional conductive heat transfer from the film front into the three phases is formulated and numerically solved to give the instantaneous rate of lateral film growth (i.e., the linear speed of the film-front) along the water/guest-fluid interface, while the film thickness is arbitrarily assumed as a fitting parameter. By comparing the predicted rates of film growth with the corresponding experimental data obtained with methane or carbon dioxide as the guest fluid, we estimated the film thickness to be about 10–20 μm for the methane hydrate at a pressure of 9.06 MPa and about 0.5 μm for the carbon-dioxide hydrate at a pressure of 5 MPa.     

Pyridylazulenes: synthesis, color changes, and structure of the colored product

A facile method for the synthesis of 1- and 2-pyridylazulenes, and of 1,3-dipyridylazulenes, is described. Color and spectral changes of these pyridylazulenes upon the addition of either acid or metal ions were investigated in detail. The color changed from blue to red upon the addition of trifluoroacetic acid or soft metal ions, depending on the substitution patterns of the pyridyl group on the azulene skeleton. The structures of the protonated or coordinated products were examined on the basis of the spectral data. It was found that the protonation or coordination of metal ions occurred on the nitrogen atom of the pyridine ring, but not on the carbon atom of azulene ring. The transition intervals of several pyridylazulenes for use as pH indicators were also determined.     

Surface and dynamic structures of bacteriorhodopsin in a 2D crystal, a distorted or disrupted lattice, as revealed by site-directed solid-state 13C NMR

The 3D structure of bacteriorhodopsin (bR) obtained by X-ray diffraction or cryo-electron microscope studies is not always sufficient for a picture at ambient temperature where dynamic behavior is exhibited. For this reason, a site-directed solid-state 13C NMR study of fully hydrated bR from purple membrane (PM), or a distorted or disrupted lattice, is very valuable in order to gain insight into the dynamic picture. This includes the surface structure, at the physiologically important ambient temperature. Almost all of the 13C NMR signals are available from [3-13C]Ala or [1-13C]Val-labeled bR from PM, although the 13C NMR signals from the surface areas, including loops and transmembrane alpha-helices near the surface (8.7 angstroms depth), are suppressed for preparations labeled with [1-13C]Gly, Ala, Leu, Phe, Tyr, etc. due to a failure of the attempted peak-narrowing by making use of the interfered frequency of the frequency of fluctuation motions with the frequency of magic angle spinning. In particular, the C-terminal residues, 226-235, are present as the C-terminal alpha-helix which is held together with the nearby loops to form a surface complex, although the remaining C-terminal residues undergo isotropic motion even in a 2D crystalline lattice (PM) under physiological conditions. Surprisingly, the 13C NMR signals could be further suppressed even from [3-13C]Ala- or [1-13C]Val-bR, due to the acquired fluctuation motions with correlation times in the order of 10(-4) to 10(-5) s, when the 2D lattice structure is instantaneously distorted or completely disrupted, either in photo-intermediate, removed retinal or when embedded in the lipid bilayers.     

The Weight-Bearing Rate on the Paretic Limb of Cerebrovascular Hemiplegic Patients Necessary for an Independent Obstacle Negotiation Gait

Purpose: The obstacle negotiation gait (ONG) is a fundamental activity of daily living. In cerebrovascular hemiplegic patients (stroke patients), the weight-bearing rate (WBR) on the paretic limb necessary for an independent ONG was studied. Methods: One hundred and seventeen stroke patients were involved. The patients'' average age at the time of the study was 67 years, and the average time from stroke onset was 102 days. There were 68 men and 49 women. Seventy patients were right hemiplegics, and 47 were left hemiplegics. The correlations between ONG and age, sex, body mass index (BMI), time from stroke onset, muscle strength of both the paretic and non-paretic limbs, Brunnstrom stage of the lower limbs, deep sensation, and the WBR on both the paretic and non-paretic limbs were studied. Patients who could perform ONG independently and safely were categorized as the independent group (IG), and those who needed observation or any assistance were categorized as the dependent group (DG). Results: The BMI, muscle strength of both the paretic and non-paretic limbs, Brunnstrom stage of the lower limbs, deep sensation and the WBR for both the paretic and non-paretic limbs were significantly different between the IG and DG groups. In particular, the WBR on the paretic limb was found to correlate significantly with the ONG, and a WBR value of 80.5% on the paretic limb gave a clear cut-off value. Conclusion: Although multiple factors influenced the ONG of stroke patients, the WBR on the paretic limb was the most influential.     

Defect-effects on the photoluminescence of ZrO2 bulk,film and nanocrystals

The photoluminescence (PL) properties of ZrO₂ have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO₂ specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO₂ film crystal on Zr ) and nanocrystals (surface area: 35–45m²/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O₂ gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO₂ nanocrystals.     

Minimization of erase-band in shingled PMR with asymmetric writer

To make the write-field much stronger with sharper cross-track field gradient in Shingled perpendicular Magnetic Recording (SMR), we have successfully developed asymmetric SMR heads with one-side shield design. Using these heads, higher track density capability on the shielded-side was demonstrated, which came from narrower erase-band width at shielded side.     

CONCEPTUAL DESIGN OF BESSEL BEAM CAVITY FOR FREE-ELECTRON LASER

The conventional cavity for a free-electron laser (FEL) oscillator usually forms an optical beam of Gaussian mode, which undergoes transverse spread along the interaction region. The transverse divergence of an optical beam will induce reduction of the FEL gain from three aspects: degenerating filling factor, causing diffraction loss and limiting the effective interaction distance. Bessel optical beam has been experimentally demonstrated diffraction-free characteristics in its propagation, which provides a possibility of improvement of FEL gain. In this paper, we present a conceptual design of a Bessel beam cavity for the free-electron laser oscillator. This cavity generates nondiffracting optical beam in the wiggler, resulting in improving the filling factor, decreasing the diffraction loss and elongating the effective interaction distance.     

Experiment on Gamma Ray Generation by Laser Compton Scattering

A gamma ray generation facility was developed through laser Compton scattering on an electron beam storage ring, for the purpose of researching nuclear transmutation. Theoretical analysis on gamma ray yield and energy spectrum was performed, as well as EGS4 simulation code was employed to simulate the interaction of gamma ray and Ge detector. The acquired experimental results are in agreement with theory.     

A new chiral 2-sulfonylamino-2′-phosphino-1,1′-binaphthyl ligand for highly enantioselective copper-catalyzed conjugate addition of diethylzinc to benzylideneacetones

A new axially chiral phosphine-sulfonamide ligand was prepared via a chiral component (R)-2-amino-2′-diphenylphosphinyl-1,1′-binaphthyl, which was conveniently synthesized through a new route involving hydrolysis of (R)-2-cyano-2′-phosphinyl-1,1′-binaphthyl followed by Hofmann rearrangement of the amide group. The new ligand was found to be very efficient in copper-catalyzed enantioselective conjugate addition of diethylzinc to acyclic enones such as benzylideneacetones, providing very high enantioselectivity up to 99% ee.