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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[4.4.0.02,4]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.  相似文献   
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Given a tree with leaf set X, there are certain ways of arranging the elements of X in a circular order so that can be embedded in the plane and ‘preserve’ this ordering. We investigate some new combinatorial properties of these ‘circular orderings.’ We then use these properties to establish two results concerning dissimilarity maps on X that are induced by edge-weighted trees with leaf set X.  相似文献   
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We investigate the combinatorics of a topological space that is generated by the set of edge-weighted finite trees. This space arises by multiplying the weights of edges on paths in trees and is closely connected to tree reconstruction problems involving finite state Markov processes. We show that this space is a contractible finite CW-complex whose face poset can be described via a partial order on semilabelled forests. We then describe some combinatorial properties of this poset, showing that, for example, it is pure, thin and contractible.  相似文献   
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We prove a linear bound on the average total curvature of the central path of linear programming theory in terms of the number of independent variables of the primal problem, and independent of the number of constraints.  相似文献   
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Dedicated to the memory of John Oxtoby  相似文献   
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We study the tangent space at a monomial point M in the Hilbert scheme that parameterizes all ideals with the same Hilbert function as M over an exterior algebra.  相似文献   
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We consider a deterministic discrete-time model of fire spread introduced by Hartnell [Firefighter! an application of domination, Presentation, in: 20th Conference on Numerical Mathematics and Computing, University of Manitoba in Winnipeg, Canada, September 1995] and the problem of minimizing the number of burnt vertices when a fixed number of vertices can be defended by firefighters per time step. While only two firefighters per time step are needed in the two-dimensional lattice to contain any outbreak, we prove a conjecture of Wang and Moeller [Fire control on graphs, J. Combin. Math. Combin. Comput. 41 (2002) 19-34] that 2d-1 firefighters per time step are needed to contain a fire outbreak starting at a single vertex in the d-dimensional square lattice for d?3; we also prove that in the d-dimensional lattice, d?3, for each positive integer f there is some outbreak of fire such that f firefighters per time step are insufficient to contain the outbreak. We prove another conjecture of Wang and Moeller that the proportion of elements in the three-dimensional grid Pn×Pn×Pn which can be saved with one firefighter per time step when an outbreak starts at one vertex goes to 0 as n gets large. Finally, we use integer programming to prove results about the minimum number of time steps needed and minimum number of burnt vertices when containing a fire outbreak in the two-dimensional square lattice with two firefighters per time step.  相似文献   
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