Determination of kinetic parameters for pyrolysis of cellulose and cellulose treated with ammonium phosphate by differential thermal analysis and thermal gravimetric analysis

Activation energy E, pre-exponential factor k₀, and reaction order n for the pyrolysis of α-cellulose and cellulose modified with dihydrogen ammonium phosphate were determined by means of TGA and DTA. The results obtained are E = 53.5 kcal./mole, k₀ = 10^18.8 min.^?1, n = 1 for α-cellulose and E = 32 kcal./mole, k₀ = 10¹² min.^?1, n = 1 for modified cellulose. A new theory of DTA was also developed. This theory, in which it is concluded that the peak value of DTA curve coincides with the maximum rate of reaction, may be used not only for the present work but is generally applicable to DTA studies. Detailed procedures of experiment and theory are described.     

Seasonal fluctuation of DNA photodamage in marine plankton assemblages at Palmer Station, Antarctica

Ultraviolet radiation-induced DNA damage frequencies were measured in DNA dosimeters and natural plankton communities during the austral spring at Palmer Station, Antarctica, during the 1999-2000 field season. We found that the fluence of solar ultraviolet-B radiation (UV-B) at the earth's surface correlated with stratospheric ozone concentrations, with significant ozone depletion observed because of "ozone hole" conditions. To verify the interdependence of ozone depletion and DNA damage in natural microbial communities, seawater was collected daily or weekly from Arthur Harbor at Palmer Station, Antarctica, throughout "ozone season," exposed to ambient sunlight between 0600 and 1800 h and fractionated using membrane filtration to separate phytoplankton and bacterioplankton populations. DNA from these fractions was isolated and DNA damage measured using radioimmunoassay. Under low-ozone conditions cyclobutane dimer concentrations in bacterioplankton and phytoplankton communities were maximal. DNA damage measured in dosimeters correlated closely with ozone concentrations and UV-B fluence. Our studies offer further support to the theory that stratospheric deozonation is detrimental to marine planktonic organisms in the Southern Ocean.     

Synthesis of tricyclic compounds as steroid 5alpha-reductase inhibitors

A series of 4-phenoxybutyric acid derivatives attached to a tricyclic skeleton were prepared and evaluated as 5alpha-reductase inhibitors. Structure activity relationships for these compounds in terms of rat epididymis (type 2) 5alpha-reductase inhibitory activities reveal that 1) the substitution pattern at the 11-position of dibenz[b,e]oxepin influenced potency, 2) higher lipophilicity of the tricyclic skeleton improved potency, whereas the existence of a basic nitrogen atom in this skeleton was detrimental to potency, and 3) isobutyl substitution at the 8 positon of the azepine skeleton was tolerated. Among the tricyclic compounds studied, 4-[3-[5-benzyl-8-(2-methyl)propyl-10,11-dihydrodibenz[b,f]azepine- 2-carboxamido]phenoxy]butyric acid (26) was the most potent inhibitor of rat type 2 5alpha-reductase at 0.1 microM.     

A three‐dimensional Cartesian cut cell method for incompressible viscous flow with irregular domains

A three‐dimensional Cartesion cut cell method is presented for the simulations of incompressible viscous flows with irregular domains. A new model (referred to as ‘6+N’ model) is proposed to describe arbitrarily shaped cut cells and treat all the cells as polyhedrons with 6+N faces. The finite volume discretization of the Navier–Stokes equation is then implemented by using the ‘6+N’ model to separate the surface flux integrals into two parts, that is, the fluxes through the basic face of the hexahedron and those through the cutting surfaces. The previously proposed Kitta Cube algorithm and volume computer‐aided design platform (J. Comput. Aided. Des. 2005; 37(4): 1509–1520. Doi:10.1016/j.cad.2005.03.006) are adopted to generate cut cells and provide shape data and physical attributes for the numerical analysis. A modified SIMPLE‐based smoothing pressure correction scheme is applied to suppress checkerboard pressure oscillations caused by the collocated arrangement of velocities and pressure. The calculation accuracy of the numerical method expressed by L₁ and L _∞ norm errors is first demonstrated by the simulation of a pipe flow. Then its feasibility, efficiency, and potential in engineering applications are verified by applying it to solve natural convections between concentric spheres and between eccentric spheres. The heat transfer patterns in eccentric spheres are also obtained by using the numerical method. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of Plasma Window for gas charge stripper at RIKEN RIBF

A differential pumping system with a Plasma Window (PW) has been developed for an application to a window-less He gas charge stripper. A PW with Southern Methodist University design was newly fabricated and tested off-line for evaluation of differential pumping efficiency. Switching gases for plasma seed from Ar to He was tested. It was found that the PW reduced the pressure at the first differential pumping section to 1/13 for Ar and to 1/17 for He, comparing with differential pumping without PW. At the second pumping section, the pressures were drastically reduced to 1/160 and to 1/4,520 for Ar and He, respectively. These pressure reduction factors indicate that one differentially pumped stage could be removed from a conventional differential pumping system.     

Hyperpolarized 13C Magnetic Resonance Imaging of Fumarate Metabolism by Parahydrogen-induced Polarization: A Proof-of-Concept in vivo Study

Hyperpolarized [1-¹³C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-¹³C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-¹³C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-¹³C]fumarate at sufficient ¹³C polarization for ex vivo detection of hyperpolarized ¹³C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo ¹³C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis.     

Nonlinear viscoelastic properties and change in entanglement structure of linear polymer

Simultaneous measurements of stress relaxation and differential dynamic modulus were made at 268 K over a time scale of 10 to 10⁴⁵ s for nearly monodisperse polybutadiene (M _w =2.2x10⁵, 1,2-structure 70%, M _e =3600) and also one having coarse cross-linking (M _c =29000). Static shear strain ranged from 0.1 to 2.0. In a long-time region (t> _k ), the relaxation modulus G (; t) could be expressed by the product G (0; t) h (y). The observed h() agreed well with the Doi-Edwards theory without use of IA approximation. Both the cured and uncured samples showed initial drop of the differential storage modulus G (), ; t) followed by gradual recovery, but did not attain the value before shearing G (, ; t) for the uncured sample showed smaller values than that for the cured one in the whole measured time scale at the higher strain, confirming the two origins of nonlinear viscoelasticity of well entangled polymer; induced chain anisotropy and induced decrement in entanglement density. G (, ; t) curves for the cured sample agreed well with the BKZ predictions. But the curves for the uncured sample agreed well with the BKZ prediction only at the time scale of t< _k . BKZ prediction showed significant upward deviations at t> _k . Such the differences are discussed in terms of the two origins.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Charge strippers for Radioisotope Beam Factory at RIKEN

The accelerator complex at the RIKEN Radioisotope Beam Factory accelerates heavy ions ranging from oxygen to uranium using triple stripping system to provide the beams at required charge. In many cases, the charge strippers cause problems during high-intensity beams accelerator operation. The charge stripper problem has been most significant during uranium beam acceleration because the lifetimes of the conventional carbon foils are extremely short. We conducted extensive R&D on the first stripper and found a solution using a low-Z gas stripper. We also plan to modify a second stripper operating recently with short-lifetime carbon foils. The stripper with better parameters will be needed when the beam intensity is increased by a new injector system for acceleration of uranium beam with higher charge.     

Filament stretching equation in Lagrangian coordinates

The general integral of the very simple equation ^21/n/() was found to describe the cross sectional area of filaments of isothermal power law fluids while in transient stretching where is time and is the initial location of fluid molecules at time = 0 given as the distance from a reference point fixed in space. Any such stretching transient given as a solution of the above equation is physically realizable subject to the restrictions > 0 and/ < 0.