Studies on cardiac ingredients of plants. VII: Chemical transformation of proscillaridin by means of the Diels-Alder reaction and biological activities of its derivatives.

The Diels-Alder reactions of a cardiac glycoside, proscillaridin (1), with some dienophiles were investigated. The reaction of 1 with alkenes such as methyl vinyl ketone and methyl acrylate afforded 3-oxo-2-oxabicyclo[2.2.2]oct-7-enes (2-5) and para-substituted benzene derivatives (6 and 7), while 1 reacted with alkynes (3-butyn-2-one, methyl propiolate) to yield para- or meta-substituted benzene derivatives (6-9). The biological activities of the resulting derivatives were evaluated by the use of isolated guinea-pig papillary muscle preparations and Na+,K(+)-adenosine triphosphatase (ATPase) preparation from dog kidney. Among the proscillaridin derivatives, compounds 4 and 7 moderately inhibited Na+,K(+)-ATPase activity. Furthermore, the concentration range of 7 over which its positive inotropic effect on guinea-pig papillary muscle preparations, increased from 5% to 95% of maximum was broader than that of 1, i.e., concentration dependency was maintained over a greater range of concentration.     

Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.     

Reduction of dislocation density and improvement of optical quality in ZnO layers by MgO-buffer annealing

Optical properties of ZnO thin films with/without MgO-buffer annealing were investigated by low and room temperature photoluminescence measurements. The ZnO films were grown on c-sapphire substrates by plasma-assisted molecular-beam epitaxy employing a thin MgO-buffer layer. Dislocation density of ZnO layer was reduced from 5.3 × 10⁹ to 1.9 × 10⁹ cm⁻² by annealing MgO-buffer prior to the growth of ZnO. The intensity of free exciton emission from the sample with MgO-buffer annealing was almost twice of that from the sample without annealing, while the deep level emission from the sample with MgO-buffer annealing was about 1/3 of that without annealing. The MgO-buffer annealing improves optical quality of overgrown ZnO films.     

Promiscuity in Antibody Catalysis: Esterolytic Activity of the Decarboxylase 21D8

The high structural similarity of decarboxylase antibody 21D8 and esterase antibody 48G7 suggests that 21D8 might also possess hydrolytic activity. Kinetic investigations show that 21D8 does promote the selective hydrolysis of methyl 4‐nitrophenyl carbonate and sodium 4‐(acetoxy)benzenesulfonate with catalytic proficiencies (k_cat/K_m)/k_un of ca. 10⁵ M ^?1. The ability of 21D8 to accelerate a reaction for which it was not developed suggests that certain antibody scaffolds are intrinsically predisposed toward catalysis, a property that can be enhanced and refined during affinity maturation in response to a transition‐state analog. At the same time, however, the restricted structural diversity of the immune system may ultimately limit the catalytic efficiency that can be achieved.     

Complex genetic evolution of artificial self‐replicators in cellular automata

It is widely believed that evolutionary dynamics of artificial self‐replicators realized in cellular automata (CA) are limited in diversity and adaptation. Contrary to this view, we show that complex genetic evolution may occur within simple CA. The evolving self‐replicating loops (“evoloops”) we investigate exhibit significant diversity in macro‐scale morphologies and mutational biases, undergoing nontrivial genetic adaptation by maximizing colony density and enhancing sustainability against other species. Nonmutable subsequences enable genetic operations that alter fitness differentials and promote long‐term evolutionary exploration. These results demonstrate a unique example of genetic evolution hierarchically emerging from local interactions between elements much smaller than individual replicators. © 2004 Wiley Periodicals, Inc. Complexity 10: 33–39, 2004     

Constructive and Destructive Two-Pulse Excitation Investigated with a White-Light Michelson Interferometer

Linear propagation of two pulses through methanol solution of aluminum phthalocyanine chloride is investigated using a modified white-light Michelson interferometer. The observed coherence time of the white light is 6 fs, and the separation between the two-excitation pulses is set to about 10 fs. The excitation is dependent on the phase-relation between the two pulses. We have observed an enhancement of the excitation when the two pulses are in-phase and strong suppression of the excitation when the two pulses are out of phase by π.     

In Situ Immobilization of Ultrafine Particles Synthesized in a Water/Oil Microemulsion

We investigated the in situ immobilization of ultrafine particles synthesized in a water/oil (w/o) microemulsion to silica for its possible application to supported metal catalysts. ZnS particles immobilized to silica by the ME method were consistent with those synthesized in a w/o microemulsion. Therefore, ZnS particles in a w/o microemulsion could be immobilized to silica without aggregation by this method. The relationship between the method of synthesizing Rh ultrafine particles in a w/o microemulsion and the diameter and diameter distribution of Rh particles immobilized to silica was studied. Rh-SiO(2) catalysts with a sharp diameter distribution could be prepared by immobilizing Rh-hydrazine complex particles because these complex particles would be very stable in a w/o microemulsion. The Rh particle diameters of Rh-SiO(2) catalysts prepared by changing the amount of silica produced were almost identical. Accordingly, the Rh particle diameter of Rh-SiO(2) catalysts could be controlled independently of Rh content by the ME method. Copyright 2001 Academic Press.