SOME PROPERTIES OF THE MAXIMUM LIKELIHOOD ESTIMATOR IN THE SIMULTANEOUS SWITCHING AUTOREGRESSIVE MODEL

Abstract. The simultaneous switching autoregressive (SSAR) model proposed by Kunitomo and Sato (A non-linearity in economic time series and disequilibrium econometric models. In Theory and Application of Mathematical Statistics (ed. A. Takemura). Tokyo:University of Tokyo Press (in Japanese), 1994; Asymmetry in economic time series and simultaneous switching autoregressive model. Struct. Change Econ. Dyn. , forthcoming (1994).) is a Markovian non-linear time series model. We investigate the finite sample as well as the asymptotic properties of the least squares estimator and the maximum likelihood (ML) estimator. Due to a specific simultaneity involved in the SSAR model, the least squares estimator is badly biased. However, the ML estimator under the assumption of Gaussian disturbances gives reasonable estimates.     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

Photocatalytic H2 evolution under visible light irradiation on Zn1-x Cu x S solid solution

The H₂ evolution reaction from an aqueous Na₂SO₃ solution proceeded with 3.7% quantum yield under visible light irradiation (λ > 420 nm) on a Zn_0.957Cu_0.043S solid solution photocatalyst without co‐catalysts such as Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

New type of tin support for hydroprocessing catalyst

TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts.     

Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

Resistance to sulfur poisoning of hot gas cleaning catalysts for the removal of tar from the pyrolysis of cedar wood

In the partial oxidation of tar derived from the pyrolysis of cedar wood, the effect of H₂S addition was investigated over non-catalyst, steam reforming Ni catalyst, and Rh/CeO₂/SiO₂ using a fluidized bed reactor. In the non-catalytic gasification, the product distribution was not influenced by the presence of H₂S. Steam reforming Ni catalyst was effective for the tar removal without H₂S addition, however, the addition of H₂S deactivated drastically. In contrast, Rh/CeO₂/SiO₂ exhibited higher and more stable activity than the Ni catalyst even under the presence of high concentration of H₂S (280 ppm). On the Ni catalyst, the adsorption of sulfur was observed by XPS and Ni species was oxidized during the partial oxidation of tar. In the case of Rh/CeO₂/SiO₂, the adsorption of sulfur was below the detection limit of XPS. This can be related to the self-cleaning of catalyst surface during the circulation in the fluidized bed reactor for the partial oxidation of tar derived from cedar pyrolysis.     

Texture and Formation Mechanism of Fibrous Calcium Hydroxyapatite Particles Prepared by Decomposition of Calcium–EDTA Chelates

The texture of fibrous calcium hydroxyapatite (Ca₁₀-(PO₄)₆(OH)₂, CaHAP) particles that were prepared by the decomposition of calcium–ethylenediaminetetraacetic acid (calcium–EDTA) chelates at 100°C under various pH conditions (pH values of 5–10) was investigated by various means. Well-crystallized fibrous CaHAPs were produced at pH .6. The stoichiometry of the CaHAPs with a chemical formula of Ca_{10− x} (HPO₄) _x (PO₄)_{6− x} (OH)_{2− x} (H₂O) _x was improved by increasing the decomposition pH. All the CaHAPs had unit-cell dimensions of a = 0.9436 ± 0.0003 nm and c = 0.6881 ± 0.0006 nm, exhibiting an enlarged a value. The finding of mesoporosity of CaHAPs by nitrogen gas (N₂) adsorption measurement indicated that the CaHAPs were produced by an agglomeration of primary particles. Furthermore, the nonstoichiometric CaHAPs that formed at pH 6 developed ultramicropores, which were accessible to water (H₂O) molecules but not to N₂ molecules, by the elimination of H₂O molecules that were adsorbed in interstices of primary particles in less-orderly crystallized CaHAPs and/or by dehydration of HPO₄²⁻ groups. These findings by gas adsorption techniques could give evidence for the agglomeration mechanism to attain a polycrystalline CaHAP, although they exhibited good crystallinity with large size.     

Guinea pig bone marrow cells treated with platelet-activating factor generate factor(s) which affects their DNA synthesis and microbicidal activity

We have previously reported that platelet-activating factor (PAF) induces proliferation and microbicidal activity of guinea pig bone marrow cells. In the present study, we have found that the conditioned medium of PAF- or nonmetabolizable PAF agonist-treated guinea pig bone marrow cells augmented DNA synthesis and induced microbicial activity of bone marrow cells. A PAF specific antagonist, CV-6209, inhibited generation of the active conditioned medium by PAF. Addition of the PAF antagonist only partially suppressed the augmentative effect of the active conditioned medium on DNA synthesis; this is consistent with the fact that, because of the rapid breakdown, no appreciable amount of PAF remained in the conditioned medium of PAF-treated cells. Although mouse bone marrow cells did not respond to PAF unlike guinea pig cells, their DNA synthesis was significantly enhanced by the conditioned medium of PAF-treated guinea pig bone marrow cells. Thus, some newly generated factor(s) distinct from the originally inoculated PAF seemed to modulate the bioactions of PAF on bone marrow cells. An appreciable amount of PAF was produced by calcium ionophore-treated guinea pig bone marrow cells. These findings indicate that PAF synthesized in guinea pig bone marrow cells induces generation in the cells of some factor(s) which affects proliferation or microbicidal activity. Presented at The Third International Conference on Platelet-Activating Factor and Structurally Related Ether Lipids, Tokyo, Japan, May 1989.     

Residues important for the function of a multihelical DNA binding domain in the new transcription factor family of Cam and Tet repressors

We report that some prokaryotic repressors including CamR andTetR belong to the same family. CamR and TetR bind to DNA usinga multihelical DNA binding domain (DBD) at the N-termini ofthe proteins, while the C-termini are important for regulatingthe DNA binding in a manner dependent on their co-factors (camphorfor CamR, tetracycline for TetR). In all, 11 important aminoacid positions have been identified in the CamR DBD by the systematicsubstitution of residues by Ala. Of the 11 positions, 10 areeither buried in the core, and thus important for creating thehydrophobic environment, or exposed on the surface, and thusimportant for binding to DNA. The eleventh residue, Gly, seemsto be important for a loop structure. The DNA binding mode ofthis type of DBD and a general mechanism of regulating theirDNA binding are discussed in reference to the crystal structureof TetR [Hinrichs et al., (1994) Science, 264, 418–420].