Synthesis of β -Cyperone via Fungal Hydroxylation of thujone-derived tricyclic cyclopropanes

Synthesis of optically active sesquiterpenes with a eudesmane C-skeleton from the chiral starting material thujone involves transformation of a tricyclic intermediate (1R,2R,4S)-1,7-dimethyl-4-(1-methylethyl)tricyclo[4.4.0.0^2,4]dec-6-en-8-one ( 2 ) into the bicyclic compound β -cyperone ( 5 ). Hydroxylation of 2 at C(5) or C(11) permits subsequent opening of the cyclopropane ring and rearrangement to β -cyperone. In this publication, studies involving hydroxylation of 2 by fungal cultures are presented. The resultant products are useful intermediates in efficient synthesis of eudesmane sesquiterpenes. Of five fungi tested, Rhizopus oryzae ATCC 11145 proved most versatile. It hydroxylates at the exocyclic C(11) position in high yield (70%) and, to a lesser extent, at C(5) (5%). Enzymatic activity appears at the end of growth phase and at least 2.2 g of 2 per liter can be metabolized without significant loss of product yield. A second fungus, Cunninghamella echinulata ATCC 9244, proved most useful for hydroxylation of derivatives of 2 for the preparation of derivatives of β -cyperone, although product yields were low (2–20%), some derivatives were nonreactive, and hydroxylation at C(9) occurred. The relationship between precursor structure and enzyme affinity is discussed.     

Three-dimensional Schwarzschild spacetimes

In the following we find all of the three-dimensional flat spacetimes which are static and rotationally symmetric.     

Electrical detection of nuclear spin echoes

We show, via a straightforward calculation, that it is feasible to detect nuclear spin echoes in a ferromagnetic thin film by electrical means. The detection scheme is based on the deflection of the electronic magnetization when the nuclear magnetization reforms during an echo. This deflection is observed as a time-dependent magnetoresistive signal.     

Elliott-Morse measures and Kakutani's dichotomy theorem

Dedicated to the memory of John Oxtoby     

Effects of metal and “magnetic wall” on the dispersion characteristic of magnetostatic waves

The dispersion relation of magnetostatic waves tangentially magnetized to saturation ferrite film, with a “magnetic wall” condition (tangential component of microwave magnetic field is equal to zero) on one of the film surface and with a metal condition on the opposite surface is analyzed. The dispersion characteristics show that unidirectional magnetostatic waves appear in this structure: they can transfer energy in one direction only and fundamentally cannot transfer energy in the opposite direction. The dispersion-free propagation of magnetostatic waves also is possible in the structure in a wide frequency interval.     

A note on acyclic domination number in graphs of diameter two

A subset S of the vertex set of a graph G is called acyclic if the subgraph it induces in G contains no cycles. S is called an acyclic dominating set of G if it is both acyclic and dominating. The minimum cardinality of an acyclic dominating set, denoted by γ_a(G), is called the acyclic domination number of G. Hedetniemi et al. [Acyclic domination, Discrete Math. 222 (2000) 151-165] introduced the concept of acyclic domination and posed the following open problem: if δ(G) is the minimum degree of G, is γ_a(G)?δ(G) for any graph whose diameter is two? In this paper, we provide a negative answer to this question by showing that for any positive k, there is a graph G with diameter two such that γ_a(G)-δ(G)?k.     

Bioaccumulation and excretion of arsenic compounds by a marine unicellular alga,polyphysa peniculus

Polyphysa peniculus was grown in artificial seawater in the presence of arsenate, arsenite, monomethylarsonate and dimethylarsinic acid. The separation and identification of some of the arsenic species produced in the cells as well as in the growth medium were achieved by using hydride generation–gas chromatography–atomic absorption spectrometry methodology. Arsenite and dimethylarsinate were detected following incubation with arsenate. When the alga was treated with arsenite, dimethylarsinate was the major metabolite in the cells and in the growth medium; trace amounts of monomethylarsonate were also detected in the cells. With monomethylarsonate as a substrate, the metabolite is dimethylarsinate. Polyphysa peniculus did not metabolize dimethylarsinic acid when it was used as a substrate. Significant amounts of more complex arsenic species, such as arsenosungars, were not observed in the cells or medium on the evidence of flow injection–microwave digestion–hydride generation–atomic absorption spectrometry methodology. Transfer of the exposed cells to fresh medium caused release of most cell–associated arsenicals to the surrounding environment.     

Gas-phase thermal decomposition of peroxy-N-butyryl nitrate

The gas-phase thermal decomposition rate of peroxy-n-butyryl nitrate (n-C₃H₇C(O)OONO₂, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH₃C(O)OONO₂, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10^?4 s^?1 for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10^?4 s^?1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. © 1994 John Wiley & Sons, Inc.