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Total synthesis of bottromycin A2 can be accomplished through a diastereoselective Mannich reaction of a chiral sulfinamide, mercury-mediated intermolecular amidination, and cyclization of a constrained tetracyclic peptide. Exploitation of this process allowed the synthesis of several novel bottromycin analogs. The antimicrobial activity of these analogs was evaluated in vitro against Gram-positive bacteria, such as methicillin resistant Staphylococcus aureus (MRSA) and vancomycin resistant enterococci (VRE). Structure–activity relationships were explored taking into consideration the unique three-dimensional structure of the compounds. Notably, one of the new analogs devoid of a methyl ester, which is known to lower the in vivo efficacy of bottromycin, exhibited antibacterial bioactivity comparable to that of vancomycin.

Full details of the initial development and continued examination of a powerful intramolecular palladium(0)-mediated indole annulation for macrocyclization closure of the strained 16-membered biaryl ring system found in complestatin (1, chloropeptin II) and the definition of factors impacting its intrinsic atropodiastereoselectivity are described. Its examination and use in an alternative, second generation total synthesis of complestatin are detailed in which the order of the macrocyclization reactions was reversed from our first generation total synthesis. In this approach and with the ABCD biaryl ether ring system in place, the key Larock cyclization was conducted with substrate 36, containing four phenols, five secondary amides, one carbamate, and four labile aryl chlorides, and provided the product 37 (56%) exclusively as a single atropisomer (>20:1, detection limits) possessing the natural (R)-configuration. In this instance, the complexity of the substrate and the reverse macrocyclization order did not diminish the atropodiastereoselectivity, rather it provided an improvement over the 4:1 selectivity that was observed with the analogous substrate used to provide the isolated DEF ring system in our first generation approach. Just as significant, the atroposelectivity represents a complete reversal of the diasteroselectivity observed with analogous macrocyclizations conducted using a Suzuki biaryl coupling.

A new NADH-fumarate reductase inhibitor, verticipyrone, was isolated from the cultured broth of a fungus, Verticillium sp. FKI-1083. The structure was established as (E)-2-methoxy-3,5-dimethyl-6-(3-methyl-2-undecenyl)-4H-pyran-4-one. Verticipyrone exhibited an IC50 value of 0.88 nM against NADH-fumarate reductase of Ascaris suum. Verticipyrone inhibited both Ascaris and bovine heart complex I, and its synthetic analogue, 8,9-dihydro-8-hydroxyverticipyrone, showed good selectivity against Ascaris complex I.

The high temperature deformation behavior of two-phase intermetallic-based alloys composed of the D0 22 -Al 3 Ti and A15-Mo 3 Al phases is investigated. It is found that the equi-axed two-phase structure formed by an isothermal heat treatment is very stable even after a high-temperature heat treatment and, moreover, the microstructure is retained even after heavy deformation at high temperature. The strain-rate sensitivity m is 0.3 or higher, and a steady state deformation is attained. Compressive deformability is found to be extremely high with the equi-axed two-phase structure. Conversely, a lamellar structure was found to be unstable during deformation. The strain-rate sensitivity m of the specimens with a lamellar structure is almost the same as that of the equi-axed two-phase structure, and the resulting microstructure strongly suggests that the deformation is concentrated at the boundaries between the lamellar colonies, where the equi-axed two-phase structure is formed during deformation by spheroidization.

The first total synthesis of chloropeptin II (1, complestatin) is disclosed. Key elements of the approach include the use of an intramolecular Larock indole synthesis for the initial macrocyclization, adopting conditions that permit utilization of a 2-bromoaniline, incorporating a terminal alkyne substituent (-SiEt(3)) that sterically dictates the indole cyclization regioselectivity, and benefiting from an aniline protecting group (-Ac) that enhances the atropdiastereoselectivity and diminishes the strained indole reactivity toward subsequent electrophilic reagents. Not only did this key reaction provide the fully functionalized right-hand ring system of 1 in superb conversion (89%) and good atropdiastereoselectivity (4:1 R:S), but it also represents the first reported example of what will prove to be a useful Larock macrocyclization strategy. Subsequent introduction of the left-hand ring system enlisting an aromatic nucleophilic substitution reaction for macrocyclization with biaryl ether formation completed the assemblage of the core bicyclic structure of 1. Intrinsic in the design of the approach and by virtue of the single-step acid-catalyzed conversion of chloropeptin II (1) to chloropeptin I (2), the route also provides a total synthesis of 2.

In Japan, the largest material exposure program “SM/MPAC&SEED (Service Module/ Micro-Particles Capturer and Space Environment Exposure Device) Experiment” has been completed. This program is quite ambitious among the other Japanese materials exposure tests; 3 sets of samples have been exposed for 1, 2 and 3 years in orbit in order to discover the fluence dependence of the material responses. We have learned a lot of lessons from this program. Based on the lessons learned, the “Advanced Material Exposure Test Working Group” has been established by the Committee on Space Utilization in 2007. This working group discussed the current problems of the material exposure program (flight tests) and proposed the future direction of the experimental methodologies. In this presentation, problems and new challenges discussed in this working group will be discussed., ISTS Special Issue: Selected papers from the 27th International Symposium on Space Technology and Science

Thermal control materials such as white paints and germanium-coated polyimide film were evaluated with respect to their space environmental tolerance for materials selection of the Dual-frequency Precipitation Radar of the Global Precipitation Measurement satellite (GPM/DPR). Though peeling off and cracking occurred in one paint material during the thermal shock test, other paints showed good tolerance against thermal shock, atomic oxygen, and ultraviolet ray irradiation. Germanium coating on polyimide film was also verified as high atomic oxygen tolerant barrier. Comparing different thickness germanium coatings, it seems that a 1000 angstrom Germanium film has fewer defects and risk of AO undercutting than a 525 angstrom Germanium film.