Improvement of a Measurement System for Surface Loss Rate of Ozone

Ozone molecules present in high-purity oxygen as a feed gas interact with surfaces and oxygen molecules in an enclosed container. Therefore, some of the ozone molecules are destroyed and the density of ozone decreases with time. An experimental system has been constructed to monitor the temporal decrease in ozone density in a container based on the HgI 254 nm photoabsorption method. Our investigation is focused on the dependence of the effective lifetime of ozone on the wall material at various gas pressures. During the experiments, distortion of the measured decay curves often caused by instabilities in the mercury lamp intensity. We thus attempted to build a simple setup that eliminates the effect of long-term intensity drift. This setup is based on light source intensity monitoring by a separate photodetector and data correction software. This article describes the setup of the experimental apparatus, the results including some preliminary experiments and the temporal variation of the surface loss rate of ozone by repeated measurement along with inspections of the wall surface by Auger electron spectroscopy.     

Synthesis of cyclic poly(methyl methacrylate) by the intramolecular cyclization of α-amino, ω-carboxyl heterodifunctional poly(methyl methacrylate)

Summary α-Amino, ω-carboxyl heterodifunctional poly(methyl methacrylate) was prepared by a living anionic polymerization of methyl methacrylate using N,N'-diphenylethylenediamine monolithium amide and succinic anhydride as an initiator and terminator, respectively. Its intramolecular cyclization was carried out to obtain a well-defined cyclic poly(methyl methacrylate). Received: 27 June 2001/Accepted: 16 July 2001     

A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

In the oxidation of cyclohexene with H₂O₂in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H₃PMo_12-xW _x O₄₀(x=0–12), several peroxo species were observed by ³¹P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM₄O₈(O₂)₈]^3-(M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H₃PMo_12-xW_xO₄₀. It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.     

Development of a microchannel catalytic reactor system

The purpose of this article is to demonstrate the applicability of microreactors for use in catalytic reactions at elevated temperatures. Microchannels were fabricated on both sides of a silicon wafer by wet chemical etching after pattern transfer using a negative photoresist. The walls of the reactor channel were coated with a platinum layer, for use as a sample catalyst, by sputtering. A heating element was installed in the channel on the opposite surface of the reactor channel. The reactor channel was sealed gas-tight with a glass plate by using an anodic bonding technique. A small-scale palladium membrane was also prepared on the surface of a 50-Μm thick copper film. In the membrane preparation, a negative photoresist was spin-coated and solidified to serve as a protective film. A palladium layer was then electrodeposited on the other uncovered surface. After the protective film was removed, the resist was again spin-coated on the copper surface, and a pattern of microslits was transferred by photolithography. After development, the microslits were electrolitically etched away, resulting in the formation of a palladium membrane as an assemblage of thin layers formed in the microslits. The integration of the microreactor and the membrane is currently under way.     

A Multiple‐Labeling Strategy for Nonribosomal Peptide Synthetases Using Active‐Site‐Directed Proteomic Probes for Adenylation Domains

Genetic approaches have greatly contributed to our understanding of nonribosomal peptide biosynthetic machinery; however, proteomic investigations are limited. Here, we developed a highly sensitive detection strategy for multidomain nonribosomal peptide synthetases (NRPSs) by using a multiple‐labeling technique with active‐site‐directed probes for adenylation domains. When applied to gramicidin S‐producing and ‐nonproducing strains of Aneurinibacillus migulanus (DSM 5759 and DSM 2895, respectively), the multiple technique sensitively detected an active multidomain NRPS (GrsB) in lysates obtained from the organisms. This functional proteomics method revealed an unknown inactive precursor (or other inactive form) of GrsB in the nonproducing strain. This method provides a new option for the direct detection, functional analysis, and high‐resolution identification of low‐abundance active NRPS enzymes in native proteomic environments.     

Capability of Utilizing CYP3A5 Polymorphisms to Predict Therapeutic Dosage of Tacrolimus at Early Stage Post-Renal Transplantation

While CYP3A5 polymorphisms are used to predict the initial dosage of tacrolimus therapy, the predictive capability of genetic information for dosing at early stage post-renal transplantation is unknown. We investigated the influence of polymorphisms over time. An initial oral dose of modified-release once-daily tacrolimus formulation (0.20 mg/kg) was administered to 50 Japanese renal transplant patients every 24 h. Stepwise multiple linear regression analysis for tacrolimus dosing was performed each week to determine the effect of patient clinical characteristics. The dose-adjusted trough concentration was approximately 70% higher for patients with the CYP3A5*3/*3 than patients with the CYP3A5*1 allele before the second pre-transplantation tacrolimus dose (0.97 (0.78–1.17) vs. 0.59 (0.45–0.87) ng/mL/mg; p < 0.001). The contribution of genetic factors (CYP3A5*1 or *3) for tacrolimus dosing showed increased variation from Day 14 to Day 28 after transplantation: 7.2%, 18.4% and 19.5% on Days 14, 21 and 28, respectively. The influence of CYP3A5 polymorphisms on the tacrolimus maintenance dosage became evident after Day 14 post-transplantation, although the tacrolimus dosage was determined based only on patient body weight for the first three days after surgery. Tacrolimus dosage starting with the initial administration should be individualized using the CYP3A5 genotype information.     

Effect of Ga2O3 on Sintering and Phase Stability of Sc2O3‐Doped Tetragonal Zirconia Prepared via Aqueous Solution Route

The effects of the presence of Ga₂O₃ on low‐temperature sintering and the phase stability of 4, 5, and 6 mol% Sc₂O₃‐doped tetragonal zirconia ceramics (4ScSZ, 5ScSZ, and 6ScSZ, respectively) were investigated. A series of zirconia sintered bodies with compositions (ZrO₂)_0.99?x(Sc₂O₃)_x(Ga₂O₃)_0.01, x = 0.04, 0.05, and 0.06 was fabricated by sintering at 1000°C to 1500°C for 1 h using fine powders that were prepared via the combination of homogeneous precipitation method and hydrolysis technique using monoclinic zirconia sols synthesized through the forced hydrolysis of an aqueous solution of zirconium oxychloride at 100°C for 168 h. The presence of 1 mol% Ga₂O₃ was effective in reducing sintering temperature necessary to fabricate dense bodies and enabled to obtain dense sintered bodies via sintering at 1100°C for 1 h. The phase stability, that is, low‐temperature degradation behavior of the resultant zirconia ceramics was determined under hydrothermal condition. The zirconia ceramics codoped with 1 mol% Ga₂O₃ and 6 mol% Sc₂O₃ (1Ga6ScZ) fabricated via sintering at 1300°C for 1 h showed high phase stability without the appearance of monoclinic zirconia phase, that is the tetragonal‐to‐monoclinic phase transformation was not observed in the 1Ga6ScZ after treatment under hydrothermal condition at 150°C for 30 h.     

Development of Novel Inhibitors for Histone Methyltransferase SET7/9 based on Cyproheptadine

The histone methyltransferase SET7/9 methylates not only histone but also non‐histone proteins as substrates, and therefore, SET7/9 inhibitors are considered candidates for the treatment of diseases. Previously, our group identified cyproheptadine, used clinically as a serotonin receptor antagonist and histamine receptor (H1) antagonist, as a novel scaffold of the SET7/9 inhibitor. In this work, we focused on dibenzosuberene as a substructure of cyproheptadine and synthesized derivatives with various functional groups. Among them, the compound bearing a 2‐hydroxy group showed the most potent activity. On the other hand, a 3‐hydroxy group or another hydrophilic functional group such as acetamide decreased the activity. Structural analysis clarified a rationale for the improved potency only by tightly restricted location and type of the hydrophilic group. In addition, a SET7/9 loop, which was only partially visible in the complex with cyproheptadine, became more clearly visible in the complex with 2‐hydroxycyproheptadine. These results are expected to be helpful for further structure‐based development of SET7/9 inhibitors.