Experimental and theoretical vibrational study of silyl trifluoromethanesulfonate, CF3SO2OSiH3

Infrared and Raman spectra were obtained for liquid silyl trifluoromethanesulfonate, a silylating agent of limited stability. The molecular geometry was optimized by means of density functional theory and M?ller-Plesset second order perturbation theory methods, using different basis sets. The optimized structure presents a gauche conformation, similar to that adopted by methyl trifluoromethanesulfonate, which was determined experimentally a short time ago. The wavenumbers for the normal modes of vibration and the corresponding force constants were also calculated, facilitating the interpretation of the vibrational data. The harmonic force constants given by theory were scaled to reproduce adequately the experimental wavenumbers.     

Two definitions of exponential dichotomy for skew-product semiflow in Banach spaces

In this paper we introduce a concept of exponential dichotomy for linear skew-product semiflows (LSPS) in infinite dimensional Banach spaces, which is an extension of the classical concept of exponential dichotomy for time dependent linear differential equations in Banach spaces. We prove that the concept of exponential dichotomy used by Sacker-Sell and Magalhães in recent years is stronger than this one, but they are equivalent under suitable conditions. Using this concept we where able to find a formula for all the bounded negative continuations. After that, we characterize the stable and unstable subbundles in terms of the boundedness of the corresponding projector along (forward/backward) the LSPS and in terms of the exponential decay of the semiflow. The linear theory presented here provides a foundation for studying the nonlinear theory. Also, this concept can be used to study the existence of exponential dichotomy and the roughness property for LSPS.

     

Kinetische Untersuchungen über die Silicium—Aryl-Spaltung mit Bromwasserstoff

Rate constants of the cleavage reaction of silicon aryl linkages with HBr were estimated for various aryl derivatives by means of NMR. A row of substituents was obtained, dependent on the cleavage rates. Correlation with theHammett function shows the electrophilic character of the reaction. The different cleavage rates give the possibility for specific cleavages of aryl groups from silanes.

     

Localization ability with bimodal hearing aids and bilateral cochlear implants

After successful cochlear implantation in one ear, some patients continue to use a hearing aid at the contralateral ear. They report an improved reception of speech, especially in noise, as well as a better perception of music when the hearing aid and cochlear implant are used in this bimodal combination. Some individuals in this bimodal patient group also report the impression of an improved localization ability. Similar experiences are reported by the group of bilateral cochlear implantees. In this study, a survey of 11 bimodally and 4 bilaterally equipped cochlear implant users was carried out to assess localization ability. Individuals in the bimodal implant group were all provided with the same type of hearing aid in the opposite ear, and subjects in the bilateral implant group used cochlear implants of the same manufacturer on each ear. Subjects adjusted the spot of a computer-controlled laser-pointer to the perceived direction of sound incidence in the frontal horizontal plane by rotating a trackball. Two subjects of the bimodal group who had substantial residual hearing showed localization ability in the bimodal configuration, whereas using each single device only the subject with better residual hearing was able to discriminate the side of sound origin. Five other subjects with more pronounced hearing loss displayed an ability for side discrimination through the use of bimodal aids, while four of them were already able to discriminate the side with a single device. Of the bilateral cochlear implant group one subject showed localization accuracy close to that of normal hearing subjects. This subject was also able to discriminate the side of sound origin using the first implanted device alone. The other three bilaterally equipped subjects showed limited localization ability using both devices. Among them one subject demonstrated a side-discrimination ability using only the first implanted device.     

Instabilities of micellar systems under homogeneous and non-homogeneous flow conditions

The rheological behavior of a cetylpyridinium chloride 100 mmol l^–1/sodium salicylate 60 mmol l^–1 aqueous solution was studied in this work under homogeneous (cone and plate) and non-homogeneous flow conditions (vane-bob and capillary rheometers), respectively. Instabilities consistent with non-monotonic flow curves were observed in all cases and the solution exhibited similar behavior under the different flow conditions. Hysteresis and the sigmoidal flow curve suggested as characteristic of systems that show constitutive instabilities were observed when running cycles of increasing and decreasing stress or shear rate, respectively. This information, together with a detailed determination of steady states at shear stresses close to the onset of the instabilities, allowed one to show unequivocally that "top and bottom jumping" are the mechanisms to trigger the instabilities in this micellar system. It is shown in addition that there is not a true plateau region in between the "top and bottom jumping". Finally, the flow behavior beyond the upturn seemed to be unstable and was found accompanied by an apparent violation of the no-slip boundary condition.     

Enantioselective synthesis of fluorinated alpha-amino acids and derivatives in combination with ring-closing metathesis: intramolecular pi-stacking interactions as a source of stereocontrol

[reaction: see text]. Hydride reduction of C=N bonds stereocontrolled by intramolecular pi-stacking interactions of 1-naphthylsulfinyl and N-aryl groups, nonoxidative Pummerer rearrangement, and ring-closing metathesis are efficiently combined in a highly stereoselective entry to enantiomerically pure cyclic and acyclic fluorinated beta-amino alcohols and alpha-amino acid derivatives, respectively.     

Existence and stability of bounded solutions for a system of parabolic equations

In this paper we study the existence and the stability of bounded solutions of the following non-linear system of parabolic equations with homogeneous Dirichlet boundary conditions: