Semiempirical and ab initio conformational analysis of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane with application of GIAO-SCF methods to NMR spectrum interpretation

The GIAO-SCF method for calculating isotropic nuclear magnetic shielding values has been utilized to explain certain features in the ¹H-NMR spectrum of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane. Population distributions of the low-energy conformers based on their ab initio energies were used to produce weighting factors for the individual calculated shielding values to calculate the weighted average of the shielding values for a complete set of conformers. The differences in ¹H chemical shifts between the hydrogens of the two methyl groups and between the axial and equatorial hydrogens in 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane were shown to be due to energy differences between the chair and boat orientations of the six-membered ring and contribution from a twist-boat conformation. Results suggest a hypothesis that intramolecular differences in chemical shift might be calculated to a greater degree of accuracy than chemical shifts calculated relative to a standard.     

Gel-drawn fibres of poly(vinyl alcohol)

Semi-crystalline gels of several samples of poly(vinyl alcohol) were made from solutions in which the polymer concentration varied from 2.0 to 15.0%. Entanglement density in the material was in this way reduced from the melt entanglement density. When gels were partially dried and drawn isothermally the maximum draw ratio increased with drawing temperature up to 11 to 14 at 140 to 180 C. A meltcast film could be drawn to 6.8 times at 140 C. Drawn material had a crystallinity of 55 to 80%, while that of isotropic material was 20 to 55%. Gels of lower initial concentration (lower entanglement density) could be drawn to greater extensions at a given draw temperature and had better mechanical properties. Young's modulus increased with draw ratio to values very close to those for polyethylene fibres drawn by the same amount. Young's modulus was independent of drawing temperature or degree of crystallinity, but on comparing drawn gels of the same draw ratio, crystallinity and crystalline orientation, those of lower entanglement density had a higher Young's modulus.     

Global structure of families of multivariable linear systems with an application to identification

The identification problem for linear stochastic systems may be stated roughly as follows: given observations on two stochastic processes which are the input and output of some unknown linear system, determine some estimate of the parameters of the system. A set of candidate linear systems which contains the “true” system is introduced, and probabilistic assumptions on the two stochastic processes turn the identification problem into the deterministic problem of minimizing some objective function over this candidate model set. If this set is a manifold, the existence of globally convergent identification algorithms hinges on the critical point behavior of the objective functions which it carries. By way of Morse Theory, the critical point behavior of objective functions on a manifold has implications with regard to the topology of the manifold. This paper analyzes the topology and critical point behavior of objective functions on a specific manifold of linear systems which appears frequently as the candidate model set in identification problems. This manifold is the set Σ of allm-input,p-output linear systems of fixed McMillan degree with real or complex coefficients. Over this manifold sits the principal bundle \(\tilde \Sigma\) of minimal realizations of systems in Σ It is shown that there exist three natural analytic metrics on the associated vector bundle. It is also shown that, in the real case, the first Stiefel-Whitney class of the bundle \(\tilde \Sigma\) has min(m, p)-1 nonvanishing powers; the same conclusion is drawn about the first Chern class of \(\tilde \Sigma\) in the complex case. These results, which follow from Morse Theory and some elementary homotopy and homology theory, imply that the category of the bundle \(\tilde \Sigma\) is at least min(m, p), and hence that the Lusternik-Schnirelmann category of Σ is at least min(m, p). It follows that canonical forms (i.e. sections of \(\tilde \Sigma\) ) may exist only when min(m, p) = 1 and that any objective function on Σ with compact sublevel sets has at least min(m, p) critical points. In particular, there exist on Σ no globally convergent gradient algorithms when min(m, p) > 1.     

Transport properties in3He-4He mixtures near the superfluid transition

We report measurements of the temperature, density, and concentration gradients in³He-⁴He mixtures, induced by a vertical heat flux. The flat horizontal cell included two superposed capacitors and the density was determined by means of the dielectric constant method. The experiments were carried out on mixtures with mole fractionsX ₃=0.37, 0.15, and 0.05 at saturated vapor pressure, with special emphasis on the region near the superfluid transition. Our measurements under steady-state conditions give the conductivity , the thermal diffusion ratiok _T , and the coefficient of thermal expansion. We describe the singular behavior of these quantities in the neighborhood ofT (X). In the superfluid phase, we test with fair success a relation by Khalatnikov between gradX/ gradT and several static properties. From the relaxation times needed to attain steady-state conditions, and in combination with measured static and transport properties, we obtain in the normal phase the mass diffusionD, which diverges strongly asT is approached. In the superfluid phase, we test successfully a scaled relation that results from the solution of Khalatnikov's hydrodynamic equations. From our data the dispersion relations for scattered light are calculated: _o/q ² in both the normal and the superfluid phases and ₂/q ² in the normal phase.Research supported by NSF grant DMR 8024056.     

Density of dilute 3He-4He solutions

The number density of dilute ³He-⁴He solutions under saturated vapor pressure is calculated within the framework of quantum hydrodynamics. For temperatures T small compared to the ³He Fermi temperature T _F, results are given for ³He concentrations large enough to manifest ³He quasiparticle interactions. The nondegenerate regime (TT _F) is also considered in the limit of small ³He concentration. Relevance to experimental determination of quasiparticle energies and interactions is emphasized.Supported by the National Science Foundation under Grant No. GP-40831.     

Definition of the Linear Region of X-Ray -Induced Cable Response

Cable response to X-rays is linear with incident fluence, provided the deposited charge in cable dielectrics is directly proportional to the X-ray flux. To estimate the level at which the linear region ends, we discuss three nonlinear processes that modify the deposited charge profile in a hypothetical cable model: field-limiting in vacuum gaps, ionization effects in air-filled gaps, and radiation-induced dielectric conductivity. The exact level at which limiting of the Norton driver in an elemental length of cable begins depends on the cable geometry and the X-ray source. Estimates of the onset of nonlinearities caused by field-limiting and by dielectric conductivity are found in terms of cable and source parameters. With air-filled gaps, the Norton driver is always nonlinear. In addition to limiting of the Norton drivers, the load response of a long cable may be limited because propagating currents are attenuated by the induced conductivity of the bulk of the dielectric.     

Effects of Coke and Formulation Variables on Fracture of Bench Scale Prebaked Anodes for Aluminum Smelting

Bench scale anodes were prepared using a number of calcined cokes, aggregate sizings, and pitch levels and tested for thermal shock resistance and flexural strength. Thermal shock resistance rose with increasing coke real density, while flexural strength tended to improve with increasing coke bulk density. With coarser aggregate sizings, a pitch level resulting in maximum baked apparent density maximized thermal shock resistance and flexural strength. With a finer aggregate sizing, thermal shock resistance and flexural strength peaked at a pitch level greater than that producing the highest baked apparent density, so maximum values require more pitch than probably practical for full-size anodes.     

Psychology for the public: A content analysis of Psychology Today..

Surveyed the extent to which Psychology Today (PT) has maintained an empirical basis for its articles and the degree to which psychologists and individuals with doctorates have been responsible for PT articles. Two samples of PT were selected for review by 2 raters (the present authors). Findings indicate that not only have PT articles significantly shifted away from a presentation of empirically based data, but the proportion of articles authored by psychologists, as well as the educational level of authors, has declined, particularly in the last 3 yrs. (4 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Dufour Gland Contents of Ants of the Cataglyphis bicolor Group

The species of desert-dwelling ants of the Cataglyphis bicolor (Hymenoptera: Formicidae) group are difficult to distinguish by morphological features. Analysis of the secretion from the Dufour glands of workers of a number of colonies was undertaken to see if it provided a clear test of species. Linked 6c-ms showed in all samples straight and branched-chain alkanes, linear alkenes, ketones, aldehydes, acetates, and a group of C₂₂ to C₂₈ esters not previously identified in this genus. Contents of the Dufour glands of C. savignyi from Tunisia and Egypt were similar, and comprised straight and branched-chain alkanes, alkenes and small amounts of esters. C. bicolor from Tunisia contained compounds similar to C. savignyi but was distinguished from the latter by larger amounts of the esters. The major compound in the glands of C. viaticus was tridecane, in contrast to the pentadecane of other species. It also contained a branched alkane, 3-methyltridecane as a major component. Branched-chain esters and a wide variety of acetates were also found in this species. C. diehlii had a limited range of compounds, with branched alkanes almost completely absent and high proportions of pentadecene and dodecyl acetate. C. bombycinus, a sympatric species, but recognized as not belonging to the bicolor group by its different mandibular gland substances, was notable in having butanoate esters in its Dufour glands. Despite these differences among species, both the great variability of individuals from a single colony and the among between conspecific colonies make species diagnosis from a few individuals difficult, in contrast with postpharyngeal glands, which, as recently reported, give a clearer indication of species.     

Proof of termination within a weak logic of programs

Summary A weak logic of programs is a formal system in which statements that mean the program halts cannot be expressed. In order to prove termination, we would usually have to use a stronger logical system. In this paper we show how we can prove termination of both iterative and recursive programs within a weak logic by augmenting the programs with counters and adding bound assertions on the counters as loop invariants and entry conditions. Thus, most of the existing verifiers which are based on a weak logic of programs can be used to prove termination of programs without any modification. We give examples of proofs of termination and of upper bounds on computation time that were obtained using a Pascal program verifier. The use of the method to locate causes of non-termination is also illustrated.This research was supported inpart by the Advanced Research Agency of the Office of the Secretary of Defence under contract DAHC 15-73-C-0435