A novel design of a levoglucosenone derived chiral auxiliary

A two-step general approach to a new chiral auxiliary starting from levoglucosenone is reported. The compound is obtained by a [4+2] cycloaddition reaction with anthracene followed by a diastereoselective reduction of the C-2 keto function in high overall yield. The auxiliary has been used as chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene and shown to be efficient for asymmetric induction.     

Speech deterioration in postlingually deafened adults

Postlinngually deafened adults reading the Rainbow Passage differed from hearing-control subjects in producing greater pitch variability and mean pitch on stressed and unstressed vowels, greater fluctuations in pitch within sentences, less correlation of intrinsic pitch with vowel height and slower temporal parameters. When reading the Phonetic Inventory Sentences, they revealed less differentiation of place of articulation in fricative and plosive consonants. The present findings, taken together with those of longitudinal and implant studies, are applied to constraining models of the role of self hearing in the elaboration of speech.     

RNA self-splicing and energy localization

We establish a mechanism for energy localization in regions of the sugar-phosphate RNA backbone which leads to the formation of transesterification or hydrolysis hot spots. In particular, our results account for the site specificity of the covalent cyclization and cycle reopening in the catalytic intervening sequence (IVS) of a ribosomal RNA.     

Speech of cochlear implant patients: a longitudinal study of vowel production.

Acoustic parameters were measured for vowels spoken in /hVd/ context by four postlingually deafened recipients of multichannel (Ineraid) cochlear implants. Three of the subjects became totally deaf in adulthood after varying periods of partial hearing loss; the fourth became totally deaf at age four. The subjects received different degrees of perceptual benefit from the prosthesis. Recordings were made before, and at intervals following speech processor activation. The measured parameters included F1, F2, F0, SPL, duration, and amplitude difference between the first two harmonic peaks in the log magnitude spectrum (H 1-H2). Numerous changes in parameter values were observed from pre- to post-implant, with differences among subjects. Many changes, but not all, were in the direction of normative data, and most changes were consistent with hypotheses about relations among the parameters. Some of the changes tended to enhance phonemic contrasts; others had the opposite effect. For three subjects, H 1-H2 changed in a direction consistent with measurements of their average air flow when reading; that relation was more complex for the fourth subject. The results are interpreted with respect to: characteristics of the individual subjects, including vowel identification scores; mechanical interactions among glottal and supraglottal articulations; and hypotheses about the role of auditory feedback in the control of speech production. Almost all the observed differences could be attributed to changes in the average settings of speaking rate, F0 and SPL, which presumably can be perceived without the need for spectral place information. Some observed F2 realignment may be attributable to the reception of spectral cues.     

2-Dimension from the Topological Viewpoint

In this paper we study the 2-dimension of a finite poset from the topological point of view. We use homotopy theory of finite topological spaces and the concept of a beat point to improve the classical results on 2-dimension, giving a more complete answer to the problem of all possible 2-dimensions of an n-point poset.      

IR multiphoton dissociation of CF3I. Pressure effect with inert and reactive gases

The IR multiphoton dissociation of CF₃I has been studied in the presence of isobutane and with isobutane and Ar and CO₂ as inert gases. The dependence of the reaction probability P(Φ) with fluence (ϕ) is confirmed. Modeling of the experimental results shows that for the energy transfer processes the average energy transferred per collision 〈†E〉_d varies with (ϕ).     

Pattern of separatrices and intrinsic reaction coordinates for degenerate thermal rearrangements

A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations.     

The Binary System BaF2/AlF3

The system BaF₂/AlF₃ is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF₅, Ba₃Al₂F₁₂, Ba₅AlF₁₉, polymorphic Ba₃AlF₉ and Ba₅AlF₁₃. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works.     

Solvent-extraction and Langmuir-adsorption-based transport in chemically functionalized nanopore membranes

We have investigated the transport properties of nanopore alumina membranes that were rendered hydrophobic by functionalization with octadecyltrimethoxysilane (ODS). The pores in these ODS-modified membranes are so hydrophobic that they are not wetted by water. Nevertheless, nonionic molecules can be transported from an aqueous feed solution on one side of the membrane, through the dry nanopores, and into an aqueous receiver solution on the other side. The transport mechanism involves Langmuir-type adsorption of the permeating molecule onto the ODS layers lining the pore walls, followed by solid-state diffusion along these ODS layers; we have measured the diffusion coefficients associated with this transport process. We have also investigated the transport properties of membranes prepared by filling the ODS-modified pores with the water-immiscible (hydrophobic) liquid mineral oil. In this case the transport mechanism involves solvent extraction of the permeating molecule into the mineral oil subphase confined with the pores, followed by solution-based diffusion through this liquid subphase. Because of this different transport mechanism, the supported-liquid membranes show substantially better transport selectivity than the ODS-modified membranes that contain no liquid subphase.