Additions of enantiopure alpha-sulfinyl carbanions to (S)-N-sulfinimines: asymmetric synthesis of beta-amino sulfoxides and beta-alphamino alcohols

The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

Can basic auditory and cognitive measures predict hearing-impaired listeners' localization and spatial speech recognition abilities?

This study aimed to clarify the basic auditory and cognitive processes that affect listeners' performance on two spatial listening tasks: sound localization and speech recognition in spatially complex, multi-talker situations. Twenty-three elderly listeners with mild-to-moderate sensorineural hearing impairments were tested on the two spatial listening tasks, a measure of monaural spectral ripple discrimination, a measure of binaural temporal fine structure (TFS) sensitivity, and two (visual) cognitive measures indexing working memory and attention. All auditory test stimuli were spectrally shaped to restore (partial) audibility for each listener on each listening task. Eight younger normal-hearing listeners served as a control group. Data analyses revealed that the chosen auditory and cognitive measures could predict neither sound localization accuracy nor speech recognition when the target and maskers were separated along the front-back dimension. When the competing talkers were separated along the left-right dimension, however, speech recognition performance was significantly correlated with the attentional measure. Furthermore, supplementary analyses indicated additional effects of binaural TFS sensitivity and average low-frequency hearing thresholds. Altogether, these results are in support of the notion that both bottom-up and top-down deficits are responsible for the impaired functioning of elderly hearing-impaired listeners in cocktail party-like situations.     

Minimizing Neumann fundamental tones of triangles: An optimal Poincaré inequality

The first nonzero eigenvalue of the Neumann Laplacian is shown to be minimal for the degenerate acute isosceles triangle, among all triangles of given diameter. Hence an optimal Poincaré inequality for triangles is derived.The proof relies on symmetry of the Neumann fundamental mode for isosceles triangles with aperture less than π/3. Antisymmetry is proved for apertures greater than π/3.     

Sobolev spaces and approximation by affine spanning systems

We develop conditions on a Sobolev function \(\psi \in W^{m,p}({\mathbb{R}}^d)\) such that if \(\widehat{\psi}(0) = 1\) and ψ satisfies the Strang–Fix conditions to order m ? 1, then a scale averaged approximation formula holds for all \(f \in W^{m,p}({\mathbb{R}}^d)\) :

$ f(x) = \lim_{J \to \infty} \frac{1}{J} \sum_{j=1}^{J} \sum_{k \in {{\mathbb{Z}}}^d} c_{j,k}\psi(a_j x - k) \quad {\rm in} W^{m, p}({{\mathbb{R}}}^d).$

The dilations { a _j } are lacunary, for example a _j =  2 ^j , and the coefficients c _j,k are explicit local averages of f, or even pointwise sampled values, when f has some smoothness. For convergence just in \({W^{m - 1,p}({\mathbb{R}}^d)}\) the scale averaging is unnecessary and one has the simpler formula \(f(x) = \lim_{j \to \infty} \sum_{k \in {\mathbb{Z}}^d} c_{j,k}\psi(a_j x - k)\) . The Strang–Fix rates of approximation are recovered. As a corollary of the scale averaged formula, we deduce new density or “spanning” criteria for the small scale affine system \(\{\psi(a_j x - k) : j > 0, k \in {\mathbb{Z}}^d \}\) in \(W^{m,p}({\mathbb{R}}^d)\) . We also span Sobolev space by derivatives and differences of affine systems, and we raise an open problem: does the Gaussian affine system span Sobolev space?

     

Gabor dual spline windows

A method is presented for constructing dual Gabor window functions that are polynomial splines. The spline windows are supported in [−1,1], with a knot at x=0, and can be taken C^m smooth and symmetric. The translation and modulation parameters satisfy a=1 and 0<b1/2. The full range 0<ab<1 is handled by introducing an additional knot. Many explicit examples are found.