COSMIC(90): An improved molecular mechanics treatment of hydrocarbons and conjugated systems

Summary Four modifications to the COSMIC molecular mechanics force field are described, which greatly increase both its versatility and the accuracy of calculated conformational energies. The Hill non-bonded van der Waals potential function has been replaced by a two-parameter Morse curve and a new H-H potential, similar to that in MM3, incorporated. Hydrocarbon energies in particular are much improved.A simple iterative Hückel pi-electron molecular orbital calculation allows modelling of conjugated systems. Calculated bond lengths and rotational barriers for a series of conjugated hydrocarbons and nitrogen heterocycles are shown to be as accurate as those determined by the MM2 SCF method.Explicit hydrogen-bonding potentials for H-bond acceptor-donor atom pairs have been included to give better hydrogen bond energies and lengths. The van der Waals radii of protonic hydrogens are reduced to 0.5 Å and the energy well depth is increased to 1.0 kcal mol^-1.Two new general atom types, N⁺ _sp ² and O^- _sp ³ , have been introduced which allow a wide variety of charged conjugated systems to be studied. A minimum of parameterisation is required, as the new types are easily included in the Hückel scheme which automatically adjusts bond and torsional parameters according to the defined bond-order relationships.     

The Small Index Property for Free Groups and Relatively Free Groups

1. Some groups with the small index property In this paper we shall use the methods of the paper [6] by Hodges,Hodkinson, Lascar and Shelah to show that the free group ofcountably infinite rank and certain relatively free groups ofcountably infinite rank have the small index property.     

Pulsed-Field-Gradient Measurements of Time-Dependent Gas Diffusion

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O₂, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10⁻⁶m²s⁻¹for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times.     

Algebras with Collapsing Monomials

A semigroup S is called collapsing if there exists a positiveinteger n such that for every subset of n elements in S, atleast two distinct words of length n on these letters are equalin S. In particular, S is collapsing whenever it satisfies alaw. Let U(A) denote the group of units of a unitary associativealgebra A over a field k of characteristic zero. If A is generatedby its nilpotent elements, then the following conditions areequivalent: U(A) is collapsing; U(A) satisfies some semigrouplaw; U(A) satisfies the Engel condition; U(A) is nilpotent;A is nilpotent when considered as a Lie algebra.     

Chemical imaging in biology and medicine using ion microscopy

The ability to quantitatively map the distribution of elements on the micrometer scale and smaller with high sensitivity and isotopic discrimination is unique to ion microscopy. The information contained in ion images can be crucial to the study of the solid state, where chemical heterogeneity is often directly related to observed behavior. The tools of digital image processing allow the extraction of quantitative information from the image data. These techniques coupled with improved instrumentation for the detection of ion images drastically increase the problem solving capabilities of the ion microscope. The use of such methods and instrumentation in the ion microscopic analyses of cell cultures and tissues of biological and biomedical relevance will be discussed.     

PARTIAL VERSUS GENERAL STORAGE POLICY: COMMODITIES AND RESOURCES

This paper examines joint storage considerations when both commodities and resources can be stored, e.g., grain and water for irrigation. Results suggest that when separate agencies control public resource and commodity storage, suboptimal storage rules occur unless (i) each agency is sensitive to the policies of the other, (ii) commodity inventories are adjusted in response to prices, and (iii) resource inventories are adjusted in response to both commodity demand and resource supply conditions. For example, the common case where water storage depends on weather and reservoir conditions alone is not sufficiently general. The results imply that water management agencies that tend to be dominated by engineers and hydrological considerations need to incorporate economic considerations into decision processes.