Preparation, Characterization and Catalysis of Intrazeolite Molybdenum, Cobalt and Cobalt–Molybdenum Sulfide Clusters: A Molecular Approach to Hydrodesulfurization Catalysts

Better understandings of the nature of Co–Mo sulfide catalysts are of great importance to a rational design of highly active hydrodesulfurization catalysts on a molecular level. Synthesis of uniform binary sulfide clusters well-defined in structure and thermally stabilized on a support is desirable for such purposes. In the present study, successful preparations, using metal carbonyls as precursors, of Mo, Co and Co–Mo sulfide clusters encaged in zeolite are reported. The structure, location and catalytic properties of the clusters are described on the basis of XPS, XAFS, XRD, XRF, IR, HREM and adsorptions of benzene and NO. Implications for the generation of catalytic synergy between Co and Mo sulfides are presented in brief. It is suggested that the host–guest interactions between zeolite framework oxygens and precursor molecules and product clusters are crucial to the size and structure of the intrazeolite clusters.     

Synthesis and structure revision of tyroscherin, and bioactivities of its stereoisomers against IGF-1-dependent tumor cells

Synthesis of the proposed structure of tyroscherin, a growth inhibitor of IGF-1-dependent cancer cells, was succeeded by one-pot Julia coupling. However, spectral data of the synthetic compound were not identical with those of natural tyroscherin. The stereochemistry of tyroscherin is revised to be 2S,3R,8R,10R by syntheses of stereoisomers. Synthetic tyroscherin showed more potent activity than its stereoisomers against IGF-1-dependent cancer cells.     

Syntheses of pyrido[1,2-a][1,3,5]triazin-4-one C-deoxyribonucleosides

We achieved the syntheses of new C-deoxyribonucleosides bearing pyrido[1,2-a][1,3,5]triazin-4-one derivatives using palladium-catalyzed Heck-type coupling. Some of these C-deoxyribonucleosides were able to convert to phosphoramidite reagents, which can be used for DNA synthesizer. DNA oligomers including pyrido[1,2-a][1,3,5]triazin-4-one C-deoxyribonucleoside, which had 2-amino group were synthesized, and T_m values with a natural nucleoside were measured.     

Infrared thermographic analysis on copolymerization of spiroorthoester with oxetane

Infrared (IR) thermography was employed to monitor temperature changes during the copolymerization of a spiroorthoester monomer with an oxetane monomer initiated with a benzyl sulfonium salt. The temperature changes in the polymerizations decreased with the increase of the initial feed ratios of the spiroorthocarbonate monomer. For instance, the temperature in the copolymerization of the equimolar mixture of both of the monomers increased only ～1 °C, whereas that in the homopolymerization of the oxetane monomer increased more than 20 °C. This result indicates that the copolymerization employing spiroorthocarbonate monomers effectively suppress temperature increase, which are responsible to shrinkage during cooling. The suppression of polymerization shrinkage by spiroorthocarbonate was also confirmed by density measurement of the polymers using a gas pycnometer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1388–1393, 2007.     

Single- and multi-objective defensive location problems on a network

This paper considers a new optimal location problem, called defensive location problem (DLP). In the DLPs, a decision maker locates defensive facilities in order to prevent her/his enemies from reaching an important site, called a core; for example, “a government of a country locates self-defense bases in order to prevent her/his aggressors from reaching the capital of the country.” It is assumed that the region where the decision maker locates her/his defensive facilities is represented as a network and the core is a vertex in the network, and that the facility locater and her/his enemy are an upper and a lower level of decision maker, respectively. Then the DLPs are formulated as bilevel 0-1 programming problems to find Stackelberg solutions. In order to solve the DLPs efficiently, a solving algorithm for the DLPs based upon tabu search methods is proposed. The efficiency of the proposed solving methods is shown by applying to examples of the DLPs. Moreover, the DLPs are extended to multi-objective DLPs that the decision maker needs to defend several cores simultaneously. Such DLPs are formulated as multi-objective programming problems. In order to find a satisfying solution of the decision maker for the multi-objective DLP, an interactive fuzzy satisfying method is proposed, and the results of applying the method to examples of the multi-objective DLPs are shown.