Studies of Hindered Rotation and Magnetic Anisotropy by 1H, 13C and 19F NMR. The Diels-Alder Adduct of N- Pentafluorophenylmaleimide and Phencyclone: A Model for Drugs.

The potent Diels-Alder diene, phencyclone, 1, reacts with N-pentafluorophenylmaleimide, 2, to form an adduct, 3, characterized by ¹H, ¹³C, and ¹⁹F NMR at 300, 75 and 282 MHz, respectively. The one-dimensional (1D) and two-dimensional (2D) ¹H and ¹³C NMR spectra of 3 at ambient temperatures imply a slow exchange limit (SEL) regime with respect to rotation of the unsubstituted bridgehead phenyl groups about severely hindered C(sp²)-C(sp³) bonds. Major non-bonded interactions are expected between the ortho protons of the C₆H₅ groups and H-1, 8 of the phenanthrenoid moiety of 3. ¹⁹F 1D and 2D (COSY) NMR spectra show that the SEL regime also obtains for rotation about the N-C₆F₅ bond of 3, with five separate fluorine signals seen, consistent with a preferred conformation in which the C₆F₅ may lie roughly perpendicular to the plane of the pyrrolidinedione moiety, and may be in the mirror symmetry plane of 3. The results are considered relevant to hindered aryl rotations in numerous Pharmaceuticals. Selected spectral data for 2 and precursors are also presented.     

Conclaves of planes in PG (4,2) and certain planes external to the Grassmannian ${\cal G}_{1,4,2} \subset$ PG(9,2)

We show that in $\operatorname{PG}(4,2)$ there exist octets $\mathcal{P} _{8}=\{\pi_{1},\,\ldots\,,\pi_{8}\}$ of planes such that the 28 intersections $\pi_{i}\cap\pi_{j}$ are distinct points. Such conclaves (see [6]) $\mathcal{P}_{8}$ of planes in $\operatorname{PG}(4,2)$ are shown to be in bijective correspondence with those planes $P$ in $\operatorname{PG}(9,2)$ which are external to the Grassmannian $\mathcal{G}_{1,4,2}$ and which belong to the orbit $\operatorname{orb}(2\gamma)$ (see [4]). The fact that, under the action of $\operatorname{GL}(5,2),$ the stabilizer groups $\mathcal{G}_{\mathcal{P}_{8}}$ and $\mathcal{G}_{P}$ both have the structure $2^{3}:(7:3)$ is thus illuminated. Starting out from a regulus-free partial spread $\mathcal{S}_{8}$ in $\operatorname{PG}(4,2)$ we also give a construction of a conclave of planes $P\in\operatorname{orb}(2\gamma)\subset\operatorname{PG}(9,2).$     

Scenario optimization

Uncertainty in the parameters of a mathematical program may present a modeller with considerable difficulties. Most approaches in the stochastic programming literature place an apparent heavy data and computational burden on the user and as such are often intractable. Moreover, the models themselves are difficult to understand. This probably explains why one seldom sees a fundamentally stochastic model being solved using stochastic programming techniques. Instead, it is common practice to solve a deterministic model with different assumed scenarios for the random coefficients. In this paper we present a simple approach to solving a stochastic model, based on a particular method for combining such scenario solutions into a single, feasible policy. The approach is computationally simple and easy to understand. Because of its generality, it can handle multiple competing objectives, complex stochastic constraints and may be applied in contexts other than optimization. To illustrate our model, we consider two distinct, important applications: the optimal management of a hydro-thermal generating system and an application taken from portfolio optimization.     

Helium cosmic ray flux measurements at Mars

The helium energy spectrum in Martian orbit has been observed by the MARIE charged particle spectrometer aboard the 2001 Mars Odyssey spacecraft. The orbital data were taken from March 13, 2002 to October 28, 2003, at which time a very intense Solar Particle Event caused a loss of communication between the instrument and the spacecraft. The silicon detector stack in MARIE is optimized for the detection of protons and helium in the energy range below , which typically includes almost all of the flux during SPEs. This also makes MARIE an efficient detector for GCR helium in the energy range of 50–. We will present the first fully normalized flux results from MARIE, using helium ions in this energy range.     

On Greene-Kleitman's theorem for general digraphs

Linial conjectured that Greene—Kleitman's theorem can be extended to general digraphs. We prove a stronger conjecture of Berge for digraphs having k-optimal path partitions consisting of ‘long’ paths. The same method yields known results for acyclic digraphs, and extensions of various theorems of Greene and Frank to acyclic digraphs.     

Application of the MC SCF method to the π → π* excitation energies of ethylene

The MC SCF method is employed to calculate the N → T and N → V π → π^* vertical excitation energies of ethylene. To obtain accurate excitation energies it is found to be necessary to utilize an expanded valence space containing two π and two π^* orbitals. Relatively small MC SCF calculations, allowing at most one-electron excitations from the sigma space, are found to yield excitation energies and spatial extents of the excited states in excellent agreement with the predictions of large multi-reference or iterative-natural-orbital CI calculations. These results show that within an MC SCF framework σ-σ correlation is unimportant for describing the π → π^* processes. We also conclude that the neglect of the effects of unlinked cluster terms in some of the CI calculations may have introduced small, but important, errors in the excitation energies and predictions of the spatial extent of the V state.