Alcohols,ethers, carbohydrates,and related compounds. II. The anomeric effect

The anomeric effect has been studied for a variety of compounds using the MM4 force field, and also using MP2/6-311++G(2d,2p) ab initio calculations and experimental data for reference purposes. Geometries and energies, including conformational, rotational barriers, and heats of formation were examined. Overall, the agreement of MM4 with the experimental and ab initio data is good, and significantly better than the agreement obtained with the MM3 force field. The anomeric effect is represented in MM4 by various explicit terms in the force constant matrix. The bond length changes are accounted for with torsion-stretch elements. The angle changes are accounted for with torsion-bend elements. The energies are taken into account with a number of torsional terms in the usual way. A torsion-torsion interaction is also of some importance. With all of these elements included in the calculation, the MM4 results now appear to be adequately accurate. The heats of formation were examined for a total of 12 anomeric compounds, and the experimental values were fit by MM4 with an RMS error of 0.42 kcal/mol.     

Approximation of operators with reproducing nonlinearities

We consider an equation of the form Au+N(u)=u in a Hilbert space and assume that the nonlinearity N is reproducing relative to a known sequence of vectors. Under this assumption the Rayleigh-Ritz-Galerkin approximations lead to a simple class of nonlinear algebraic eigenvalue problems.In a general variational case we show that Lusternik-Schnirelmann critical values of Rayleigh-Ritz-Galerkin problems provide upper bounds to those of the original problem. Lower bounds are constructed in the case N(u)=B^*(Bu)³.The author would like to thank the European Research Office for their assistance in this research.     

Cytotoxic and NF-κB inhibitory sesquiterpene lactones from Piptocoma rufescens

Six new (1-6) and eight known germacranolide-type sesquiterpene lactones, along with several known phenylpropanol coumarates and methylated flavonoids, were isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. The new compounds were identified by analysis of their spectroscopic data, with the molecular structure of 3 being established by single-crystal X-ray diffraction. The absolute configurations of the sesquiterpene lactones isolated were determined from their CD and NOESY NMR spectra, together with the analysis of Mosher ester reactions. Bioassay screening results showed the majority of the sesquiterpene lactones isolated (1-13) to be highly cytotoxic toward the HT-29 human colon cancer cell line, with the most potent compound being 15-deoxygoyazensolide (10, IC(50), 0.26 μM). In addition, several of the sesquiterpene lactones exhibited NF-κB (p65) inhibitory activity.     

Translation planes of large dimension admitting nonsolvable groups

In this article, the question is considered whether there exist finite translation planes with arbitrarily small kernels admitting nonsolvable collineation groups. For any integerN, it is shown that there exist translation planes of dimension >N and orderq ³ admittingGL(2,q) as a collineation group.     

A cryogenic underground observatory for rare events: CUORE, an update

CUORE is a proposed tightly packed array of 1000 TeO₂ bolometers, each being a cube 5 cm on a side with a mass of 750 g. The array consists of 25 vertical towers, arranged in a square of 5 towers by 5 towers, each containing ten layers of four crystals. The design of the detector is optimized for ultralow-background searches for neutrinoless double beta decay of ¹³⁰Te (33.8% abundance), cold dark matter, solar axions, and rare nuclear decays. A preliminary experiment involving 20 crystals of various sizes (MIBETA) has been completed, and a single CUORE tower is being constructed as a smaller scale experiment called CUORICINO. The expected performance and sensitivity, based on Monte Carlo simulations and extrapolations of present results, are reported.     

Hybridization of optical phonons with double quantum-wire plasmons including drift instabilities

We examine the collective mode spectrum for a double quantum-wire system embedded in semi-infinite polar medium, taking account of the role of optical phonons in interaction with the double quantum-wire plasmons and bulk/surface plasmons. The collective mode frequencies are exhibited as functions of q_x (wavenumber parallel to the wires) and as functions of z₀ (distance of first wire from the interface). We also find that the region of drift instability of the collective modes is split into two disjoint regions of instability by the optical phonons, with a region of stability between them.     

A Pilot Survey of Vocal Health in Young Singers

The objective of this study was to determine the incidence of vocal problems in young choir singers and to correlate vocal problems with demographic and behavioral information. A questionnaire addressing vocal habits and hygiene was offered to 571 young choir singers, up to 25 years of age, who sing at least weekly; 129 (22.6%) responded. More than one-half of the respondents had experienced vocal difficulty, particularly older adolescents. Detrimental behaviors and circumstances surveyed were not reflective of the incidence of vocal difficulty, except for morning hoarseness, chronic fatigue, insomnia, and female gender after puberty. Voice care professionals should be aware that self-reported voice difficulties are common among young choral singers, especially postpubescent girls, and children with symptoms consistent with reflux (morning hoarseness) and emotional stress (insomnia). Laryngologists should communicate with choral conductors and singing teachers to enhance early identification and treatment of children with voice complaints, and to develop choral educational strategies that help decrease their incidence.     

Quantum insights from null-strut geometrodynamics

We discuss quantum insights due to the null-strut formalism. These insights deal primarily with two topics: the formalism of a theory of canonical simplicial quantum gravity based on the geometrodynamic duality of null-strut calculus, and the natural implementation of spinors and spin networks in null-strut calculus.