A novel bisnorditerpenelactone from Mikania hirsutissima

A novel bisnorkaurenic acid-type diterpenelactone, named mikanialactone (1), was isolated along with five known kaurenic acid-type diterpenes (2-6) from the aerial parts of Mikania hirsutissima DC (Compositae). The structure of the new bisnorditerpene was determined by spectroscopic means.     

Trajectory of the spectral/structural rearrangements for photo-oxidative reaction of neat ketoprofen and its cyclodextrin complex

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Ketoprofen is a nonsteroidal anti-inflammatory drug used as mohrus tape which causes unwanted photosensitivity due to UV irradiation. In...     

Attenuation of weak shock waves along pseudo-perforated walls

In order to attenuate weak shock waves in ducts, effects of pseudo-perforated walls were investigated. Pseudo-perforated walls are defined as wall perforations having a closed cavity behind it. Shock wave diffraction and reflection created by these perforations were visualized in a shock tube by using holographic interferometer, and also by numerical simulation. Along the pseudo-perforated wall, an incident shock wave attenuates and eventually turns into a sound wave. Due to complex interactions of the incident shock wave with the perforations, the overpressure behind it becomes non-uniform and its peak value can locally exceed that behind the undisturbed incident shock wave. However, its pressure gradient monotonically decreases with the shock wave propagation. Effects of these pseudo-perforated walls on the attenuation of weak shock waves generated in high speed train tunnels were studied in a 1/250-scaled train tunnel simulator. It is concluded that in order to achieve a practically effective suppression of the tunnel sonic boom the length of the pseudo-perforation section should be sufficiently long. Received 23 June 1997 / Accepted 16 September 1997     

Deterministic random walks on finite graphs

The rotor‐router model, also known as the Propp machine, is a deterministic process analogous to a random walk on a graph. Instead of distributing tokens to randomly chosen neighbors, the Propp machine deterministically serves the neighbors in a fixed order by associating to each vertex a “rotor‐router” pointing to one of its neighbors. This paper investigates the discrepancy at a single vertex between the number of tokens in the rotor‐router model and the expected number of tokens in a random walk, for finite graphs in general. We show that the discrepancy is bounded by O (mn) at any time for any initial configuration if the corresponding random walk is lazy and reversible, where n and m denote the numbers of nodes and edges, respectively. For a lower bound, we show examples of graphs and initial configurations for which the discrepancy at a single vertex is Ω(m) at any time (> 0). For some special graphs, namely hypercube skeletons and Johnson graphs, we give a polylogarithmic upper bound, in terms of the number of nodes, for the discrepancy. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 46,739–761, 2015     

Residual-stress determination by single-axis holographic interferometry and hole drilling—Part I: Theory

A method is described for the rapid, accurate determination of residual stresses from a holographic interference fringe pattern. The pattern is generated by the displacement field caused by localized relief of residual stresses via the introduction of a small, shallow hole into the surface of a component or test specimen. The theoretical development of the holographic method is summarized. An example is given showing how the method can be applied to a typical experimentally observed fringe pattern to determine principal residual stresses and directions.     

Clockwise-counterclockwise differentiation on the upper rim of a monofunctional gamma-cyclodextrin: efficient topological control in the syntheses of capped cyclodextrins

Intramolecular condensation of 6(A)-(N-dansyl-l-cysteine)-gamma-cyclodextrin occurred only at 6(B)-OH of the many OH groups to afford the corresponding lactone with an exo-topology.     

Crystal structure and peroxidase activity of myoglobin reconstituted with iron porphycene

The incorporation of an artificially created metal complex into an apomyoglobin is one of the attractive methods in a series of hemoprotein modifications. Single crystals of sperm whale myoglobin reconstituted with 13,16-dicarboxyethyl-2,7-diethyl-3,6,12,17-tetramethylporphycenatoiron(III) were obtained in the imidazole buffer, and the 3D structure with a 2.25-A resolution indicates that the iron porphycene, a structural isomer of hemin, is located in the normal position of the heme pocket. Furthermore, it was found that the reconstituted myoglobin catalyzed the H2O2-dependent oxidations of substrates such as guaiacol, thioanisole, and styrene. At pH 7.0 and 20 degrees C, the initial rate of the guaiacol oxidation is 11-fold faster than that observed for the native myoglobin. Moreover, the stopped-flow analysis of the reaction of the reconstituted protein with H2O2 suggested the formation of two reaction intermediates, compounds II- and III-like species, in the absence of a substrate. It is a rare example that compound III is formed via compound II in myoglobin chemistry. The enhancement of the peroxidase activity and the formation of the stable compound III in myoglobin with iron porphycene mainly arise from the strong coordination of the Fe-His93 bond.     

Catalytic enantioselective allylation of ketoimines

A general catalytic allylation of simple ketoimines was developed using 1 mol % of CuF.3PPh(3) as catalyst, 1.5 mol % of La(O(i)Pr)(3) as the cocatalyst, and stable and nontoxic allylboronic acid pinacol ester as the nucleophile. This reaction constituted a good template for developing the first catalytic enantioselective allylation of ketoimines. In this case, using LiO(i)Pr as the cocatalyst produced higher enantioselectivity and reactivity than La(O(i)Pr)(3). Thus, using the CuF-cyclopentyl-DuPHOS complex (10 mol %) and LiO(i)Pr (30 mol %) in the presence of (t)BuOH (1 equiv) produced high enantioselectivity up to 93% ee from a range of aromatic ketoimines. Mechanistic studies indicated that LiO(i)Pr accelerates the reaction by increasing the concentration of an active nucleophile, allylcopper.     

Do-it-yourself computational astronomy

We overview our GRAPE (GRAvity PipE) and GRAPE-DR project to develop dedicated computers for astrophysical N-body simulations. The basic idea of GRAPE is to attach a custom-build computer dedicated to the calculation of gravitational interaction between particles to a general-purpose programmable computer. By this hybrid architecture, we can achieve both a wide range of applications and very high peak performance. GRAPE-6, completed in 2002, achieved the peak speed of 64 Tflops. The next machine, GRAPE-DR, will have the peak speed of 2 Pflops and will be completed in 2008. We discuss the physics of stellar systems, evolution of general-purpose high-performance computers, our GRAPE and GRAPE-DR projects and issues of numerical algorithms.