Akira Fujita

Previously, we reported the specific occurrence of neutralizing autoantibodies against granulocyte-macrophage colony-stimulating factor (GM-CSF) in the bronchoalveolar lavage fluid from 11 Japanese patients with idiopathic pulmonary alveolar proteinosis (I-PAP). The autoantibody was also detected in sera from all 5 I-PAP patients examined. To determine that the existence of the autoantibody is not limited to the Japanese patients, we examined sera from 24 I-PAP patients in five countries and showed that the autoantibody was consistently and specifically present in such patients. Thus, detection of the autoantibody in sera can be used for diagnosis of I-PAP. To establish a simple and convenient method for diagnosis of I-PAP, we developed a novel latex agglutination test using latex beads coupled with recombinant human GM-CSF. GM-CSF binding proteins isolated from the sera using the latex beads were identified as the autoantibodies of IgG(1) and IgG(2). The titer of the autoantibody determined by this test correlated with that determined by ELISA. Agglutination was positive in 300-fold diluted sera from all 24 I-PAP patients, but negative in sera from four secondary PAP patients, two congenital PAP patients, 40 patients with other lung diseases, and 38 of 40 normal subjects. These results establish that the latex agglutination test is a reliable method for serological diagnosis of I-PAP with high sensitivity (100%) and specificity (98%).

BACKGROUND: Hepatitis B (HB) virus (HBV) infection is often reactivated, leading to severe hepatitis and death. Because the actual incidence of such complications is unknown, the authors surveyed hospitals to record the incidence of these complications and to identify clinical parameters that would possibly predict the development of hepatic complications. METHODS: First, 250 hospitals, belonging to the Japanese Society of Clinical Hematology, were surveyed for hematologic patients with chronic hepatitis or those with asymptomatic hepatitis virus infection in whom severe hepatitis related to chemotherapy occurred between 1987 and 1991. Second, 117 hospitals that responded to the first questionnaire were surveyed for HBV carriers without severe hepatitis who were prescribed chemotherapy. RESULTS: One-half the number of patients with severe hepatitis were HBV carriers. The incidence of severe hepatitis (52.7%) and the mortality rate (23.6%) were extremely high in HBV carriers. The incidence of severe hepatitis was significantly higher in patients with chronic hepatitis or those receiving corticosteroids (P < 0.05). The mortality rate was significantly lower in patients who were positive for hepatitis Be antigen (HBeAg) and negative for the antibody to HBeAg (anti-HBe), compared with findings in other patients (P < 0.05). CONCLUSIONS: HBV infection is a major causal agent for severe hepatitis related to chemotherapy in Japanese individuals. Chemotherapy, including corticosteroids, to treat hematologic malignancies should be considered risky in HBV carriers, especially those with chronic hepatitis or serologies negative for HBeAg and positive for anti-HBe.

Carotenoids are the precursors of important fragrance compounds in flowers of Osmanthus fragrans Lour. var. aurantiacus, which exhibit the highest diversity of carotenoid-derived volatiles among the flowering plants investigated. A cDNA encoding a carotenoid cleavage enzyme, OfCCD1, was identified from transcripts isolated from flowers of O. fragrans Lour. It is shown that the recombinant enzymes cleave carotenes to produce alpha-ionone and beta-ionone in in vitro assays. It was also found that carotenoid content, volatile emissions, and OfCCD1 transcript levels are subjected to photorhythmic changes and principally increased during daylight hours. At the times when OfCCD1 transcript levels reached their maxima, the carotenoid content remained low or slightly decreased. The emission of ionones was also higher during the day; however, emissions decreased at a lower rate than the transcript levels. Moreover, carotenoid content increased from the first to the second day, whereas the volatile release decreased, and the OfCCD1 transcript levels displayed steady-state oscillations, suggesting that the substrate availability in the cellular compartments is changing or other regulatory factors are involved in volatile norisoprenoid formation. Furthermore, the sensory evaluation of the aroma of the model mixtures suggests that the proportionally higher contribution of alpha-ionone and beta-ionone to total volatile emissions in the evening is probably the reason for the increased perception by humans of the scent emission of Osmanthus flowers.

In this paper we report on the isolation, structural characterization, and reactivity of a series of lanthanide ketyl complexes, which are generated by reactions of benzophenone and fluorenone with several different types of lanthanide reducing agents including Ln(OAr)2(L)x (Ar = C6H2-tBu2-2,6-Me-4; 1a: Ln = Sm, L = THF, x = 3; 1b: Ln = Yb, L = THF, x = 3; 1c: Ln = Sm, L = HMPA, x = 2; 1d: Ln = Yb, L = HMPA, x = 2), (C5Me5)2Ln(THF)2 (Ln = Sm, Yb), (C5Me5)Sm(OAr)(HMPA)2, Sm(N(SiMe3)2)2(THF)2, and Ln/HMPA (Ln = Sm, Yb) (HMPA = hexamethylphosphoric triamide). Reactions of 1a−d with 1 equiv of fluorenone in THF afforded the corresponding ketyl complexes Ln(OAr)2(ketyl)(L)2 (3a−d) in 85−90% isolated yields. Hydrolysis of 3a (Ln = Sm, L = THF) gave the corresponding pinacol-coupling product, 1,2-bis(biphenyl-2,2'-diyl)ethane-1,2-diol (4), while air oxidation of 3a yielded fluorenone almost quantitatively. Reaction of 3a with 1 equiv of 1a followed by hydrolysis afforded fluorenol quantitatively. When 3a was dissolved in hexane/ether, pinacol-coupling of the ketyl unit occurred to give the OEt2-coordinated pinacolate complex [Sm(OAr)2(OEt2)]2[μ-pinacolate] (5a, pinacolate = 1,2-bis(biphenyl-2,2'-diyl)ethane-1,2-diolate). Dissolving 5a in THF regenerated 3a via C−C bond cleavage of the pinacolate unit, showing that the pinacol-coupling process was reversible. Addition of 2 equiv of HMPA (per Sm) to a THF solution of 3a or 5a gave the corresponding HMPA-coordinated ketyl complex 3c. Complex 3c was more stable than 3a, and no reaction was observed when 3c was treated similarly with hexane/ether. Reactions of fluorenone with (C5Me5)2Ln(THF)2 (Ln = Sm, Yb) and (C5Me5)Sm(OAr)(HMPA)2 gave the corresponding ketyl complexes (C5Me5)2Ln(ketyl)(THF) (3e: Ln = Sm, 3f: Ln = Yb) and (C5Me5)Sm(OAr)(ketyl)(HMPA) (3i), respectively. In contrast, the similar reaction of Sm(N(SiMe3)2)2(THF)2 with fluorenone in THF yielded the pinacolate complex [Sm(N(SiMe3)2)2(THF)]2[μ-pinacolate] (5b) as the only isolable product, although the formation of a ketyl species was evident in THF solution. Reaction of 4 equiv of HMPA with 5b in THF gave a mixture of Sm(N(SiMe3)2)2(ketyl)(HMPA)2 (3k) and [Sm(N(SiMe3)2)2(HMPA)]2[μ-pinacolate] (5c), while reactions of 5b with 4 equiv of ArOH (Ar = C6H2-tBu2-2,6-Me-4) in THF and THF/HMPA produced the corresponding ArO-ligated ketyl complexes 3a and 3c, respectively. A variable-temperature UV−vis spectroscopic study in toluene derived a dissociation enthalpy of 11 kcal/mol for 5b. Reactions of metallic Ln (Ln = Sm, Yb) with 3 equiv of fluorenone and 3 equiv of HMPA in THF yielded the corresponding tris(ketyl)metal complexes Ln(ketyl)3(HMPA)3 (7a: Ln = Sm, 7b: Ln = Yb). Hydrolysis of 7a,b afforded the pinacol 4, while reaction of 7a with 0.5 equiv of 4 or benzopinacol produced the fluorenoxide/pinacolate complex 6. Reaction of 4 with Sm(N(SiMe3)2)3 in THF/HMPA also afforded 6. In contrast to the reactions of fluorenone, the similar reactions of the above reducing agents with benzophenone did not afford a structurally characterizable ketyl species, and in the case of 1d, the corresponding hydrogen radical abstraction product Yb(OCHPh2)2(OAr)(HMPA)2 (2) was isolated.

Abstract Wood‐based epoxy resins were synthesized from resorcinol‐liquefied wood. Wood was first liquefied in the presence of resorcinol with or without a sulfuric acid catalyst at high temperature. Because of the hydroxyl groups, the resorcinol‐liquefied wood was considered as a precursor for synthesizing wood‐based epoxy resin. Namely, the phenolic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition. By the glycidyl etherification, epoxy functionality was introduced to the liquefied wood. The epoxy functionality of the resins was controlled by the concentration of phenolic OH groups in the liquefied wood, which would be a dominant factor for crosslink density and properties of the cured epoxy resins. The flexural strength (150–180 MPa) and the modulus of elasticity (3.2 GPa) of the highly crosslinked wood‐based epoxy resin were equivalent to those of the commercially available epoxy resin, diglycidyl ether of bisphenol A (DGEBA). Also, the shear adhesive strength of the wood‐based epoxy resin was higher than that of DGEBA when plywood was used as the adhesive substrates. The mechanical and adhesive properties suggested that the wood‐based epoxy resins would be well suited for matrix resins of natural plant‐fiber reinforced composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2285–2292, 2006