Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

3-D vertical ray shooting and 2-D point enclosure, range searching, and arc shooting amidst convex fat objects

We present a new data structure for a set of n convex simply-shaped fat objects in the plane, and use it to obtain efficient and rather simple solutions to several problems including (i) vertical ray shooting—preprocess a set of n non-intersecting convex simply-shaped flat objects in 3-space, whose xy-projections are fat, for efficient vertical ray shooting queries, (ii) point enclosure—preprocess a set C of n convex simply-shaped fat objects in the plane, so that the k objects containing a query point p can be reported efficiently, (iii) bounded-size range searching— preprocess a set C of n convex fat polygons, so that the k objects intersecting a “not-too-large” query polygon can be reported efficiently, and (iv) bounded-size segment shooting—preprocess a set C as in (iii), so that the first object (if exists) hit by a “not-too-long” oriented query segment can be found efficiently. For the first three problems we construct data structures of size O(λ_s(n)log³n), where s is the maximum number of intersections between the boundaries of the (xy-projections) of any pair of objects, and λ_s(n) is the maximum length of (n, s) Davenport-Schinzel sequences. The data structure for the fourth problem is of size O(λ_s(n)log²n). The query time in the first problem is O(log⁴n), the query time in the second and third problems is O(log³n + klog²n), and the query time in the fourth problem is O(log³n).

We also present a simple algorithm for computing a depth order for a set as in (i), that is based on the solution to the vertical ray shooting problem. (A depth order for , if exists, is a linear order of , such that, if K₁, K₂ and K₁ lies vertically above K₂, then K₁ precedes K₂.) Unlike the algorithm of Agarwal et al. (1995) that might output a false order when a depth order does not exist, the new algorithm is able to determine whether such an order exists, and it is often more efficient in practical situations than the former algorithm.     

A simple low-vacuum environmental cell.

The environmental cell device discussed in this paper provides a modest low-vacuum scanning electron microscopy (SEM) capability to a standard SEM without requiring additional pumping. This environmental cell confines a volume of low vacuum in contact with the sample surface using a container that has an aperture for admitting the primary electron beam. The aperture is large enough to permit a limited field of view of the sample, and small enough to limit the outflow of gas into the SEM chamber to that which can be accommodated by the standard SEM pumping system. This environmental cell also functions as a gaseous detector device.     

A new Löwenheim-Skolem theorem

This paper establishes a refinement of the classical Löwenheim-Skolem theorem. The main result shows that any first order structure has a countable elementary substructure with strong second order properties. Several consequences for Singular Cardinals Combinatorics are deduced from this.

     

Geometric algebra techniques for general relativity

Geometric (Clifford) algebra provides an efficient mathematical language for describing physical problems. We formulate general relativity in this language. The resulting formalism combines the efficiency of differential forms with the straightforwardness of coordinate methods. We focus our attention on orthonormal frames and the associated connection bivector, using them to find the Schwarzschild and Kerr solutions, along with a detailed exposition of the Petrov types for the Weyl tensor.