The Role of Methoxy Group in the Nazarov Cyclization of 1,5-bis-(2-Methoxyphenyl)-1,4-Pentadien-3-one in the Gas Phase and Condensed Phase

ESI-protonated 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one (1) undergoes a gas-phase Nazarov cyclization and dissociates via expulsions of ketene and anisole. The dissociations of the [M + D]⁺ ions are accompanied by limited HD scrambling that supports the proposed cyclization. Solution cyclization of 1 was effected to yield the cyclic ketone, 2,3-bis-(2-methoxyphenyl)-cyclopent-2-ene-1-one, (2) on a time scale that is significantly shorter than the time for cyclization of dibenzalacetone. The dissociation characteristics of the ESI-generated [M + H]⁺ ion of the synthetic cyclic ketone closely resemble those of 1, suggesting that gas-phase and solution cyclization products are the same. Additional mechanistic studies by density functional theory (DFT) methods of the gas-phase reaction reveals that the initial cyclization is followed by two sequential 1,2-aryl migrations that account for the observed structure of the cyclic product in the gas phase and solution. Furthermore, the DFT calculations show that the methoxy group serves as a catalyst for the proton migrations necessary for both cyclization and fragmentation after aryl migration. An isomer formed by moving the 2-methoxy to the 4-position requires relatively higher collision energy for the elimination of anisole, as is consistent with DFT calculations. Replacement of the 2-methoxy group with an OH shows that the cyclization followed by aryl migration and elimination of phenol occurs from the [M + H]⁺ ion at low energy similar to that for 1.

Semiclassical Asymptotics and Gaps in the Spectra of Magnetic Schrödinger Operators

In this paper, we study an L ² version of the semiclassical approximation of magnetic Schrödinger operators with invariant Morse type potentials on covering spaces of compact manifolds. In particular, we are able to establish the existence of an arbitrary large number of gaps in the spectrum of these operators, in the semiclassical limit as the coupling constant goes to zero.     

Chern Character in Twisted K-Theory: Equivariant and Holomorphic Cases

 It was argued in [25, 5] that in the presence of a nontrivial B-field, D-brane charges in type IIB string theories are classified by twisted K-theory. In [4], it was proved that twisted K-theory is canonically isomorphic to bundle gerbe K-theory, whose elements are ordinary Hilbert bundles on a principal projective unitary bundle, with an action of the bundle gerbe determined by the principal projective unitary bundle. The principal projective unitary bundle is in turn determined by the twist. This paper studies in detail the Chern-Weil representative of the Chern character of bundle gerbe K-theory that was introduced in [4], extending the construction to the equivariant and the holomorphic cases. Included is a discussion of interesting examples. Received: 10 January 2002 / Accepted: 9 December 2002 Published online: 25 February 2003 RID="⋆" ID="⋆" The authors acknowledge the support of the Australian Research Council Communicated by R.H. Dijkgraaf     

The Novikov Conjecture for Low Degree Cohomology Classes

We outline a twisted analogue of the Mishchenko–Kasparov approach to prove the Novikov conjecture on the homotopy invariance of the higher signatures. Using our approach, we give a new and simple proof of the homotopy invariance of the higher signatures associated to all cohomology classes of the classifying space that belong to the subring of the cohomology ring of the classifying space that is generated by cohomology classes of degree less than or equal to 2, a result that was first established by Connes and Gromov and Moscovici using other methods. A key new ingredient is the construction of a tautological C* _r (, )-bundle and connection, which can be used to construct a C* _r (, )-index that lies in the Grothendieck group of C* _r (, ), where is a multiplier on the discrete group corresponding to a degree 2 cohomology class. We also utilise a main result of Hilsum and Skandalis to establish our theorem.     

On generalized entropy measures and pathways

Product probability property, known in the literature as statistical independence, is examined first. Then generalized entropies are introduced, all of which give generalizations to Shannon entropy. It is shown that the nature of the recursivity postulate automatically determines the logarithmic functional form for Shannon entropy. Due to the logarithmic nature, Shannon entropy naturally gives rise to additivity, when applied to situations having product probability property. It is argued that the natural process is non-additivity, important, for example, in statistical mechanics [C. Tsallis, Possible generalization of Boltzmann-Gibbs statistics, J. Stat. Phys. 52 (1988) 479-487; E.G.D. Cohen, Boltzmann and Einstein: statistics and dynamics—an unsolved problem, Pramana 64 (2005) 635-643.], even in product probability property situations and additivity can hold due to the involvement of a recursivity postulate leading to a logarithmic function. Generalized entropies are introduced and some of their properties are examined. Situations are examined where a generalized entropy of order α leads to pathway models, exponential and power law behavior and related differential equations. Connection of this entropy to Kerridge's measure of “inaccuracy” is also explored.     

Preparation and characterization of 1,2,3‐triazole‐cured polymers from endcapped azides and alkynes

Fourteen commercial polyols have been characterized by GPC, NMR spectroscopy, and elemental analysis. From these, eight corresponding tosylates, six nitrate esters, seven mesylates, 13 alkynes, and 14 azides have been prepared and all these derivatives have been fully characterized. Five alkyne monomers and eight azide monomers were also prepared. Twelve alkynes and 13 azides (functionality 2–4) were combined in 1,3‐dipolar cycloaddition reactions under neat conditions to prepare triazole‐cured polymers, avoiding any heavy metal catalyst. Characterization by NMR spectroscopy, elemental analysis, and gel permeation chromatography indicated triazole polymers 14 , 22 , 23 , 28 , and 30 with degrees of polymerization of 17–28 to be the best candidates for future work. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 238–256, 2008     

A mathematical model of medial consonant identification by cochlear implant users

The multidimensional phoneme identification model is applied to consonant confusion matrices obtained from 28 postlingually deafened cochlear implant users. This model predicts consonant matrices based on these subjects' ability to discriminate a set of postulated spectral, temporal, and amplitude speech cues as presented to them by their device. The model produced confusion matrices that matched many aspects of individual subjects' consonant matrices, including information transfer for the voicing, manner, and place features, despite individual differences in age at implantation, implant experience, device and stimulation strategy used, as well as overall consonant identification level. The model was able to match the general pattern of errors between consonants, but not the full complexity of all consonant errors made by each individual. The present study represents an important first step in developing a model that can be used to test specific hypotheses about the mechanisms cochlear implant users employ to understand speech.     

Thermal and dielectric studies of nickel malonate dihydrate single crystals

Single crystals of nickel malonate dihydrate were grown by the gel technique, employing the single diffusion method. Thermal dehydration of the crystal was investigated by thermogravimetric and differential thermal analyses. The title compound exhibits a steady thermal behaviour at higher temperature range of 350-800 °C. The dielectric properties of the prepared sample were analyzed as a function of frequency in the range of 1 kHz-1 MHz and at temperatures between 40 and 140 °C.     

On a generalised Connes-Hochschild-Kostant-Rosenberg theorem

The central result of this paper is an explicit computation of the Hochschild and cyclic homologies of a natural smooth subalgebra of stable continuous trace algebras having smooth manifolds X as their spectrum. More precisely, the Hochschild homology is identified with the space of differential forms on X, and the periodic cyclic homology with the twisted de Rham cohomology of X, thereby generalising some fundamental results of Connes and Hochschild-Kostant-Rosenberg. The Connes-Chern character is also identified here with the twisted Chern character.     

Inequalities for the Novikov-Shubin invariants

In this paper, we prove that the Novikov-Shubin invariants satisfy a sequence of inequalities and deduce some useful consequences of this result.