Further Characterization of 394-GHz Gyrotron FU CW GII with Additional PID Control System for 600-MHz DNP-SSNMR Spectroscopy

A 394-GHz gyrotron, FU CW GII, has been designed at the University of Fukui, Japan, for dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR) experiments at 600-MHz ¹H resonant frequency. After installation at the Institute for Protein Research (IPR), Osaka University, Japan, a PID feedback control system was equipped to regulate the electron gun heater current for stabilization of the electron beam current, which ultimately achieved stabilization of output power when operating in continuous wave (CW) mode. During exploration to further optimize operating conditions, a continuous tuning bandwidth of approximately 1 GHz was observed by varying the operating voltage at a fixed magnetic field. In the frequency range required for positive DNP enhancement, the output power was improved by increasing the magnetic field and the operating voltage from their initial operational settings. In addition, fine tuning of output frequency by varying the cavity cooling water temperature was demonstrated. These operating conditions and ancillary enhancements are expected to contribute to further enhancement of SSNMR signal.     

Direct Measurement of Positronium HyperFine Structure: ～ A New Horizon of Precision Spectroscopy Using Gyrotrons ～

Positronium is an ideal system for research on QED, especially in a bound state. A discrepancy (3.9σ) is found recently between measured HFS values and the QED prediction (including up-to O(α ³ log α ^− 1), where α is the fine-structure constant.). It might be due to a contribution of unknown new physics or common systematic problems in all the previous measurements. A new method to measure HFS directly is performed using a high power gyrotron. The transition from ortho-positronium to para-positronium has been observed with 5 σ CL, which is the first observation of M1 transition in (sub)Terahertz region. New technologies of high power gyrotrons are developed for precision spectroscopy.     

The Direct Spectroscopy of Positronium Hyperfine Structure Using a Sub-THz Gyrotron

Positronium is an ideal system for research on Quantum Electrodynamics (QED), especially in a bound state. A discrepancy of 3.9 standard deviations has been found between the measured hyperfine structure (Ps-HFS) and the QED predictions. This may be due to the contribution of unknown new physics or common systematic effects in previous measurements, in all of which the Zeeman effect was used. We propose a new method to directly measure the Ps-HFS using a high power gyrotron. We compare two resonators which have been developed to supply sufficient power to drive the direct transition, a Fabry-Pérot resonator and a ring resonator with a diffraction grating. We plan to perform first direct measurement of Ps-HFS within the next six months.     

Acceleration of the redox kinetics of VO2+/VO2 + and V3+/V2+ couples on carbon paper

The redox kinetics of VO²⁺/VO₂ ⁺ and V³⁺/V²⁺ couples on a carbon paper (CP, HCP030 N, Shanghai Hesen, Ltd., China) electrode were investigated in terms of their standard rate constant (k ₀) and reaction mechanism. The values determined for k ₀ for VO²⁺ ?? VO₂ ⁺ and V³⁺ ?? V²⁺ using the CP electrode are 1.0 × 10^?3 and 1.1 × 10^?3 cm s^?1, respectively. The value of k ₀ increases by one or two order(s) of magnitude compared with values obtained using electrodes composed of pyrolytic graphite and glassy carbon. The acceleration of the redox kinetics of vanadium ions is a result of the large surface area of the CP electrode. An inner-sphere mechanism for the reaction on the surface of the electrode is proposed. The kinetic features of vanadium redox reactions on the CP electrode reveal that CP is suitable for use as the electrodes in vanadium redox-flow batteries.     

A quantum chemical study on the polycondensation reaction of polyesters: The mechanism of catalysis in the polycondensation reaction

We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate) (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is investigated as a model system by using the B3LYP level of theory, and Sb(OEt)₃, Ge(OEt)₄ and Ti(OEt)₄ are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of 11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu)₄. Because the other mechanisms gave much higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by antimony, germanium and titanium alkoxides.     

Polar-Polar Interaction and Boundary Phase Structure Between Reinforcement and Matrix in a Polymer Composite

This paper describes an attempt to correlate the nature of polar-polar interaction between the reinforcement and matrix in a polymer composite with the boundary phase structure formed in contact with the reinforcement. It is shown by analyzing the mechanical dispersion data that the reinforcement-matrix interaction of Kevlar fiber reinforced poly(hydroxypropyl ether of bisphenol A) (P) is increased by blending poly(ethylene oxide) (E) or poly(ethylene adipate) (A) as a part of matrix, and that E is more efficient than A for the increase of the interaction. These results can be supported at the molecular level from the inspection of the Fourier transform infrared spectra on the Kevlar fiber coated with matrix polymers and the mixture of matrix polymers with benzanilide, which is used as a model compound of Kevlar fiber. It can be shown from the electron spectroscopy for chemical analysis on the films of PIE and P/A blend polymers formed on nylon 6 substrate (N), which is also used as a model material for the reinforcement, that A concentrates on the N-facing side for P/A film and that E concentrates on the air-facing side for PIE film. This result indicates the different susceptibility between P/A and PIE blends to the surface force from N, and hence, it likewise indicates the different interaction with the reinforcement in each blend, as shown by the mechanical dispersion data.     

Shear-induced pre-crystallization structures of long chain branched polypropylene under steady shear flow near the melting temperature

Shear-induced crystallization of a long chain hyper-branched polypropylene (LCB-PP, denoted PP-3) was carried out at a relatively high temperature of 170 °C, close to its melting temperature of 158 °C. Small-angle X-ray scattering (SAXS) showed that the intensity ratio of the normal to the perpendicular to the shear (V/H) was always larger than 1 for PP-3, indicating that shish-like structures were predominately formed and further growth to kebab was suppressed in PP-3. The crystallization behavior of PP-3 can be explained by the nature of PP-3 that there were a large amount of crystallization nuclei due to their branching points, and the point-like precursors formed from these nuclei were arrayed linearly along the shear direction and transformed into thread-like precursors or premature shishs; however, owing to the large amount of branching, further progress in crystallization was suppressed.     

防冻型黏土质可塑料的研制

为了提高可塑料的抗冻结能力,以粒度为6～3、3～1、≤1 mm的焦宝石(w(Al2O3)>45%,w(SiO2)<52%)和粒度≤45μm的黏土(w(Al2O3)>26%,w(SiO2)<65%)为原料,加入硫酸铝溶液、水和乙二醇防冻液制备出防冻型黏土质可塑料.将试样放入零下15℃的试验箱中冷冻,在室温下放置至室温,再经110℃干燥和1 000℃热处理后,分别测试试样的线变化率、抗折强度、耐压强度和体积密度,并与常温20℃下放置的试样的各项性能加以比较.结果表明:试样经过110℃和1 000℃热处理后,普通可塑料试样在零下15℃冻结后的强度比正常未冻结试样的下降约20%,而防冻型可塑料与正常试样相比,在强度方面几乎没有改变.     

Characterization of the ybdT gene product of Bacillus subtilis: Novel fatty acid β-hydroxylating cytochrome P450

We have characterized the gene encoding fatty acid α-hydroxylase, a cytochrome P450 (P450) enzyme, from Sphingomonas paucimobilis. A database homology search indicated that the deduced amino acid sequence of this gene product was 44% identical to that of the ybdT gene product that is a 48 kDa protein of unknown function from Bacillus subtilis. In this study, we cloned the ybdT gene and characterized this gene product using a recombinant enzyme to clarify function of the ybdT gene product. The carbon monoxide difference spectrum of the recombinant enzyme showed the characteristic one of P450. In the presence of H₂O₂, the recombinant ybdT gene product hydroxylated myristic acid to produce β-hydroxyristic acid and α-hydroxymyristic acid which were determined by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry. The amount of these products increased with increasing reaction period and amount of H₂O₂ in the reaction mixture. The amount of β-hydroxyl product was slightly higher than that of α-hydroxyl product at all times during the reaction. However, no reaction products were detected at any time or at any concentration of H₂O₂ when heat-inactivated enzyme was used. HPLC analysis with a chiral column showed that the β-hydroxyl product was nearly enantiomerically pure R-form. These results suggest that this P450 enzyme is involved in a novel biosynthesis of β-hydroxy fatty acid.     

Catalytic reforming of natural gas for hydrogen production in a pilot fluidized-bed membrane reactor: Mapping of operating and feed conditions

A fluidized-bed membrane reformer was operated in two independent laboratories to map various operating conditions, to investigate the effects of changing the composition of the natural gas feed stream and to verify earlier experimental trials. Two feed natural gases were tested, containing either 95.5 or 90.1 mol% of methane (3.6 or 9.9 mol% of other gaseous higher hydrocarbons). Experimental tests investigated the influence of total membrane area, reactor pressure, permeate pressure and natural gas feed rates. A permeate-H₂-to reactor natural gas feed molar ratio >2.3 was achieved with six two-sided membrane panels under steam reforming conditions and a pressure differential across the membranes of 785 kPa. The total cumulative reforming time reached 395 h, while hydrogen purity exceeded 99.99% during all tests.