First Higher‐Order Photocycloaddition to a CN Bond: 1,3‐Diazepines from Maleimides

A light touch is all that is required to cleave a maleimide C? N bond to effect a [5+2] photocycloaddition with a sterically encumbered C?N moiety (see scheme).

     

Simulation of multiphase flows in porous media

The ability to numerically simulate single phase and multiphase flow of fluids in porous media is extremely important in developing an understanding of the complex phenomena governing the flow. The flow is complicated by the presence of heterogeneities in the reservoir and by phenomena such as diffusion, dispersion, and viscous fingering. These effects must be modeled by terms in coupled systems of nonlinear partial differential equations which form the basis of the simulator. The simulator must be able to handle both single and multiphase flows and the transition regimes between the two. A discussion of some of the aspects of modeling dispersion and viscous fingering is presented along with directions for future work.The partial differential equation models are convection-dominated and contain important local effects. An operator-splitting technique is used to address these different effects accurately. Convection is treated by time stepping along the characteristics of the associated pure convection problem, and diffusion is modeled via a Galerkin method for single phase flow and a Petrov-Galerkin technique for multiphase regimes. ELLAM (Eulerian-Lagrangian Localized Adjoint Methods) are discussed to effectively treat the advection-dominated processes. Accurate approximations of the fluid velocities needed in the Eulerian-Lagrangian time-stepping procedure are obtained by mixed finite element methods. Adaptive local grid refinement techniques are then indicated to resolve important local phenomena around wells and large heterogeneities or to resolve the moving internal boundary layers which often govern the mass transfer between phases.     

Large-scale flow structures in a planar offset attaching jet with a co-flowing wall jet

Conditional averaging techniques were used to examine the periodic motions that were observed in flows consisting of an offset planar jet and a co-flowing planar wall jet. The offset jet is one jet height (H_j) away from the wall and has a Reynolds number of approximately 40, 000, based on H_j and flow-rate averaged velocity U_o; for the co-flowing jets, different heights (i.e., 0.18H_j and 0.5H_j) and velocities (i.e., 0.56U_o and 0.36U_o) were considered. The flows had periodic motions with frequencies fH_j/U_o = 0.28 and 0.49 or fH_c/U_o = 0.23 and 0.25, where H_c is the distance between the jets. The periodic motions were present in both the inner shear layer of the offset jet above the re-circulation region and the outer shear layer of the wall jet below the re-circulation region. The motions from the inner shear layer of the offset jet persisted in the shear layer that formed downstream of the re-circulating region. There were periodic motions in the outer shear layer of the offset jet particularly in the flow with the smaller wall jet. The relative contribution of the motions to the total fluctuations increased as the flow evolved downstream reaching a maximum approximately 4H_c downstream of the flow exit. The relative contribution of the periodic motions to the turbulent fluctuations was similar in the two flows but the periodic motions had a much larger impact on the near-wall velocity and pressure fluctuations in the flow with the smaller wall jet due to the trajectory of the periodic structures, the distance of the periodic structures to the wall and the size of these structures.     

Electrochemical and alkali metal reduction studies of silicon,germanium, and tin derivatives of cyclooctatetraene : Properties conferred by cyclooctatetraenide dianions by group IV substituents

The electrochemical behavior of trimethylsilyl-, trimethylgermyl-, trimethylstannyl- and t-butylcyclooctatetraenes has been examined by the techniques of polarography and cyclic voltammetry in THF and hexamethylphosphoramide (vastly preferred) solutions. Chemical reduction by means of potassium in ND₃ has also been studied. Evidence is presented that all four compounds undergo reduction to their respective dianions. However, the energetics of (Me₃)MCOT^? and (Me₃)MCOT^2? formation vary widely, as do the rates and mechanism of dianion disappearance under the conditions of electrochemical measurement. The available kinetic data suggest, for example, that destruction of the t-Bu and trimethylgermyl substituted dianions proceeds via protonation and/or disproportionation pathways. In contrast, the silyl and stannyl examples experience metal-ring carbon cleavage reactions at yet faster rates. Interestingly, the E¹_{$\text{1}\text{2}$} values give evidence of being quite well correlated by σ_p. Furthermore, when the magnitude of the E¹_{$\text{1}\text{2}$}-E²_{$\text{1}\text{2}$} gap are plotted vs the covalent radii of the M atoms, a straight line is obtained for the Si, Ge and Sn examples; C deviates widely. This effect is believed to have its origin in resonance of the M←C_π type involving the d orbitals of M which, of course, is not possible in the carbon case. The significance of these results as well as the other observations made in the course of this work is discussed.     

Infrared spectroscopy of SO2 aqueous solutions

The chemistry of SO2 solutions was studied with infrared transmission and total internal reflection (ATR) spectroscopy. The cross-sections of the SO2 stretching vibrations v1, v3 and the combination band of v1 + v3 were obtained and found to be slightly different from their gas phase values. Six features we associate with sulfur-containing ions were observed. We present the first infrared evidence for the bisulfite ion HOSO2- through detection of its OH stretching vibration. Other features may be associated with HSO3-, another isomer of the bisulfite ion, and a new compound we propose to be H2S2O6(2-). We found no evidence for sulfurous acid H2SO3.     

On the structure of water—alcohol and ammonia—alcohol protonated clusters

Collision-induced dissociation (CID) of protonated ammonia-alcohol and water-alcohol heteroclusters was studied using a triple quadrupole mass spectrometer with a corona discharge atmospheric pressure ionization source. CID results suggested that the ammonia-alcohol clusters had NH: at the core of the cluster and that hydrogen-bonded alcohol molecules solvated this central ion. In contrast, CID results in water-alcohol clusters showed that water loss was strongly favored over alcohol loss and that there was a preference for the charge to reside on an alcohol molecule. The results also indicated that a loose chain of hydrogen-bonded molecules was formed in the water-alcohol clusters and that there appeared to be no rigid protonation site or a fixed central ion. (J Am Soc Mass     

Structures and properties of linear Cn molecules

Total energies, bond lengths, charge distributions, electronic configurations, and cohesive energies are calculated for linear C_n clusters, n = 2–6. The calculations are done at the single determinant Hartree-Fock level using both double-zeta and double-zeta plus polarization basis sets.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

DOCK 4.0: Search strategies for automated molecular docking of flexible molecule databases

In this paper we describe the search strategies developed for docking flexible molecules to macomolecular sites that are incorporated into the widely distributed DOCK software, version 4.0. The search strategies include incremental construction and random conformation search and utilize the existing Coulombic and Lennard-Jones grid-based scoring function. The incremental construction strategy is tested with a panel of 15 crystallographic testcases, created from 12 unique complexes whose ligands vary in size and flexibility. For all testcases, at least one docked position is generated within 2 Å of the crystallographic position. For 7 of 15 testcases, the top scoring position is also within 2 Å of the crystallographic position. The algorithm is fast enough to successfully dock a few testcases within seconds and most within 100 s. The incremental construction and the random search strategy are evaluated as database docking techniques with a database of 51 molecules docked to two of the crystallographic testcases. Incremental construction outperforms random search and is fast enough to reliably rank the database of compounds within 15 s per molecule on an SGI R10000 cpu.