A Solid-State 11B NMR and Computational Study of Boron Electric Field Gradient and Chemical Shift Tensors in Boronic Acids and Boronic Esters

The results of a solid-state 11B NMR study of a series of 10 boronic acids and boronic esters with aromatic substituents are reported. Boron-11 electric field gradient (EFG) and chemical shift (CS) tensors obtained from analyses of spectra acquired in magnetic fields of 9.4 and 21.1 T are demonstrated to be useful for gaining insight into the molecular and electronic structure about the boron nucleus. Data collected at 21.1 T clearly show the effects of chemical shift anisotropy (CSA), with tensor spans (Ω) on the order of 10−40 ppm. Signal enhancements of up to 2.95 were achieved with a DFS-modified QCPMG pulse sequence. To understand the relationship between the measured tensors and the local structure better, calculations of the 11B EFG and magnetic shielding tensors for these compounds were conducted. The best agreement was found between experimental results and those obtained from GGA revPBE DFT calculations. A positive correlation was found between Ω and the dihedral angle (CCBO), which describes the orientation of the boronic acid/ester functional group relative to an aromatic system bound to boron. The small boron CSA is discussed in terms of paramagnetic shielding contributions as well as diamagnetic shielding contributions. Although there is a region of overlap, both Ω and the 11B quadrupolar coupling constants tend to be larger for boronic acids than for the esters. We conclude that the span is generally the most characteristic boron NMR parameter of the molecular and electronic environment for boronic acids and esters, and show that the values result from a delicate interplay of several competing factors, including hydrogen bonding, the value of CCBO, and the electron-donating or withdrawing substituents bound to the aromatic ring.Natural Sciences and Engineering Research Council (NSERC) of Canada and the Canada Foundation for Innovation

Three IT-Business Alignment Profiles: Technical Resource, Business Enabler, and Strategic Weapon

There is a growing recognition among alignment researchers and IT professionals that one size does not fit all. In this article, we provide an important extension of alignment research that shows three profiles linking IT to different business objectives. We address the need to identify the appropriate types of IT alignment by using a multi-method study including interviews and cases. Two dimensions define the three alignment profiles: internal IT-business integration and external market engagement. The technical resource profile calls for low levels of IT-business integration and IT-market engagement. The business enabler profile deploys IT in some business processes and begins engaging IT with customers and suppliers. The strategic weapon profile uses IT to mobilize and extend the enterprise, which requires extensive IT deployment, both internally and externally. Each profile differs in strategies, criteria, capabilities, and mental models. Importantly, IT decision-makers should not adopt stage-model thinking which assumes that technical resource profiles naturally progress up the chain. Rather, successful use of IT requires specifying the requisite alignment profile as an initial design decision so that appropriate levels of resource allocation and management involvement occur

Physical characteristics and non-keplerian orbital motion of "propeller" moons embedded in Saturn's rings

We report the discovery of several large "propeller" moons in the outer part of Saturn's A ring, objects large enough to be followed over the 5-year duration of the Cassini mission. These are the first objects ever discovered that can be tracked as individual moons, but do not orbit in empty space. We infer sizes up to 1--2 km for the unseen moonlets at the center of the propeller-shaped structures, though many structural and photometric properties of propeller structures remain unclear. Finally, we demonstrate that some propellers undergo sustained non-keplerian orbit motion. (Note: This arXiv version of the paper contains supplementary tables that were left out of the ApJL version due to lack of space).Comment: 9 pages, 4 figures; Published in ApJ

The MHD Kelvin-Helmholtz Instability II: The Roles of Weak and Oblique Fields in Planar Flows

We have carried out high resolution MHD simulations of the nonlinear evolution of Kelvin-Helmholtz unstable flows in 2 1/2 dimensions. The modeled flows and fields were initially uniform except for a thin shear layer with a hyperbolic tangent velocity profile and a small, normal mode perturbation. The calculations consider periodic sections of flows containing magnetic fields parallel to the shear layer, but projecting over a full range of angles with respect to the flow vectors. They are intended as preparation for fully 3D calculations and to address two specific questions raised in earlier work: 1) What role, if any, does the orientation of the field play in nonlinear evolution of the MHD Kelvin-Helmholtz instability in 2 1/2 D. 2) Given that the field is too weak to stabilize against a linear perturbation of the flow, how does the nonlinear evolution of the instability depend on strength of the field. The magnetic field component in the third direction contributes only through minor pressure contributions, so the flows are essentially 2D. Even a very weak field can significantly enhance the rate of energy dissipation. In all of the cases we studied magnetic field amplification by stretching in the vortex is limited by tearing mode, ``fast'' reconnection events that isolate and then destroy magnetic flux islands within the vortex and relax the fields outside the vortex. If the magnetic tension developed prior to reconnection is comparable to Reynolds stresses in the flow, that flow is reorganized during reconnection. Otherwise, the primary influence on the plasma is generation of entropy. The effective expulsion of flux from the vortex is very similar to that shown by Weiss for passive fields in idealized vortices with large magnetic Reynolds numbers. We demonstrated that thisComment: 23 pages of ApJ Latex (aaspp4.sty) with 10 figures, high resolution postscript images for figs 4-9 available through anonymous at ftp://ftp.msi.umn.edu/pub/twj To appear in the June 10, 1997 Ap

Interaction of ethylbenzene and styrene with iron oxide model catalyst films at low coverages: a NEXAFS study

The adsorption of ethylbenzene and styrene on well ordered epitaxial iron oxide model catalyst films with different stoichiometries was investigated using near edge X-ray absorption fine structure spectroscopy (NEXAFS). On the iron-terminated Fe3O4(111) and a?Fe2O3(0001) surfaces a chemisorption of ethylbenzene and styrene is observed which initially occurs on the iron sites via the p-electron system of the phenyl ring. This forces the molecules into an almost flat lying configuration (h6 like ring adsorption geometry). In the case of ethylbenzene this adsorption complex is supposed to lead to an activation of the C-H bonds thus facilitating the dehydrogenation to styrene. The tilt angle of the aromatic ring systems increase to about 40° when approaching monolayer saturation. In contrast, the interaction with the oxygen-terminated FeO(111) surface is weak and of the physisorption type. The adsorbate-adsorbate interaction dominates and causes a tilted adsorption of the molecules from the beginning