A new approach to the synthesis of cyclic ethers via the intermolecular allylation of α-acetoxy ethers and ring-closing metathesis

A concise synthesis of the isolaurepinnacin skeleton 6 was achieved via the intermolecular allylation of the α-acetoxy ether 3 followed by ring-closing metathesis. This methodology was successfully applied to the convergent synthesis of the oxocene 15, an advanced synthetic intermediate for the total synthesis of laurencin.     

Measurement of prompt charm meson production cross sections in pp collisions at square root s = 1.96 TeV

We report on measurements of differential cross sections dsigma/dp(T) for prompt charm meson production in ppmacr; collisions at sqrt[s]=1.96 TeV using 5.8+/-0.3 pb(-1) of data from the CDF II detector at the Fermilab Tevatron. The data are collected with a new trigger that is sensitive to the long lifetime of hadrons containing heavy flavor. The charm meson cross sections are measured in the central rapidity region |y|K-pi(+), D(*+)-->D0pi(+), D+-->K-pi(+)pi(+), D(+)(s)-->phipi(+), and their charge conjugates. The measured cross sections are compared to theoretical calculations.     

Laser-driven vehicles – from inner-space to outer-space

Laser-supported propulsion of a micro-airplane with a water-covered ablator is demonstrated. The repetitive use of an overlay structure is experimentally demonstrated with a specially designed water supply. Various transparent overlays are investigated by the CIP-based hydrodynamic code and by experiments using a pendulum and using a semi-conductor load cell. A momentum-coupling efficiency of ∼10⁴ N s/MJ is achieved by water–exotic-target experiments, in agreement with the simulation code, which predicts a maximum efficiency of ∼10⁵ N s/MJ. The concept of laser-supported propulsion can also be used for driving a Mach 5 airplane in the stratosphere, a micro-ship inside the human body, and a robot in a nuclear power reactor accident, during which large numbers of neutrons make electronic devices useless. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-3/5734-2165, E-mail: yabe@mech.titech.ac.jp     

Electrospray ion-trap multistage mass spectrometry for characterisation of co-monomer compositional distribution of bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) at the molecular level

We report an electrospray ionisation multistage mass spectrometry (ESI-MSn) method that utilises molecular mass information for determination of sequence distribution and chemical structure of mass-selected macromolecules of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) biopolyester, PHBH. On the basis of ESI-MSn studies of PHBH oligomers obtained by partial alkaline depolymerisation of natural PHBH containing 13-14 mol% of hydroxyhexanoate (HH) units, the microstructure of this bacterial copolyester was assessed up to the level of 28 repeat units. The subtle structural details of the PHBH were evaluated based on sequencing of individual macromolecular ions thus showing the utility of this technique for the analysis of biological copolyester macromolecules. It was confirmed that both HH and hydroxybutyrate (HB) units of the PHBH copolymer are randomly distributed.     

Novel fluorescent isoquinoline pigments, panaefluorolines A-C from the cultured mycobiont of a lichen, Amygdalaria panaeola

Novel fluorescent substances, named panaefluorolines A-C (1-3), were isolated from the cultured mycobiont of a lichen, Amygdalaria panaeola. These structures were elucidated on the basis of spectroscopic data, especially 2D NMR.     

Green oxidation with aqueous hydrogen peroxide

Aqueous H2O2 is an ideal oxidant, when coupled with a tungstate complex and a quaternary ammonium hydrogensulfate as an acidic phase-transfer catalyst. It oxidizes alcohols, olefins, and sulfides under organic solvent- and halide-free conditions in an economically, technically, and environmentally satisfying manner.     

Synthesis and evaluation of 6-nitro-7-(1-piperazino)quinazolines: dual-acting compounds with inhibitory activities toward both tumor necrosis factor-alpha (TNF-alpha) production and T cell proliferation

We investigated the chemical modifications of the nitroquinazoline derivative (1) through the replacement of the NH group at the C(4)-position with several N-alkyl groups to increase the lipophilicity at the C(4)-position. Among them, we found that the N-methyl analogue (5a) showed a 2-fold loss in the inhibitory activity toward tumor necrosis factor-alpha (TNF-alpha) production in vitro as compared with the NH analogue (1); however, 5a exhibited an oral inhibitory activity on TNF-alpha production with an ED50 value of 26 mg/kg, whereas 1 did not. Moreover, the oral bioavailability of 5a was higher than that of 1 (1, F=1%; 5a, F=21%), and the calculated ClogP value for 5a was higher than that for 1. These results suggest that the improved lipophilicity of 5a compared with that of 1 reflects its greater inhibitory activity on TNF-alpha production in vivo as well as oral bioavailability.     

Amide conformational switching induced by protonation of aromatic substituent

[reaction: see text] Introduction of an electron-withdrawing group on the aromatic ring of N-methylacetanilide decreased the ratio of the cis conformer, and the ratio correlates well with the Hammett sigma values of the substituents. These steric properties can be applied to achieve amide conformational switching by protonation at the aromatic substituent of 4-[bis(dimethylamino)]-N-methylacetanilide or N-[p-(dimethylamino)phenyl]-N-phenylacetamide.     

Fermi-Pasta-Ulam beta model: boundary jumps, Fourier's law, and scaling

We examine the interplay of surface and volume effects in systems undergoing heat flow. In particular, we compute the thermal conductivity in the Fermi-Pasta-Ulam beta model as a function of temperature and lattice size, and scaling arguments are used to provide analytic guidance. From this we show that boundary temperature jumps can be quantitatively understood, and that they play an important role in determining the dynamics of the system, relating soliton dynamics, kinetic theory, and Fourier transport.