k-Hankel Gabor Transform and Its Applications to the Theory of Localization Operators

Analysis Mathematica - We introduce and study the k-Hankel Gabor transform. We investigate the localization operators for this transform. In particular, we study their trace class properties and we...     

Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

Effective field and the Bloch-Siegert shift at bichromatic excitation of multiphoton EPR

The dynamics of multiphoton transitions in a two-level spin system excited by transverse microwave and longitudinal RF fields with the frequencies ω_mw and ω_rf, respectively, is analyzed. The effective time-independent Hamiltonian describing the “dressed” spin states of the “spin + bichromatic field” system is obtained by using the Krylov-Bogoliubov-Mitropolsky averaging method. The direct detection of the time behavior of the spin system by the method of nonstationary nutations makes it possible to identify the multiphoton transitions for resonances ω₀ = ω_mw + rω_rf (ω₀ is the central frequency of the EPR line, r = 1, 2), to measure the amplitudes of the effective fields of these transitions, and to determine the features generated by the inhomogeneous broadening of the EPR line. It is shown that the Bloch-Siegert shifts for multiphoton resonances at the inhomogeneous broadening of spectral lines reduce only the nutation amplitude but do not change their frequencies.     

Acoustic Analysis of Pathological Voices Compressedwith MPEG System

The MPEG-1 Layer 3 compression schema of audio signal, commonly known as mp3, has caused a great impact in recent years as it has reached high compression rates while conserving a high sound quality. Music and speech samples compressed at high bitrates are perceptually indistinguishable from the original samples, but very little was known about how compression acoustically affects the voice signal. A previous work with normal voices showed a high fidelity at high-bitrate compressions both in voice parameters and the amplitude-frequency spectrum. In the present work, dysphonic voices were tested through two studies. In the first study, spectrograms, long-term average spectra (LTAS), and fast Fourier transform (FFT) spectra of compressed and original samples of running speech were compared. In the second study, intensities, formant frequencies, formant bandwidths, and a multidimensional set of voice parameters were tested in a set of sustained phonations. Results showed that compression at high bitrates (96 and 128 kbps) preserved the relevant acoustic properties of the pathological voices. With compressions at lower bitrates, fidelity decreases, introducing some important alterations. Results from both works, Gonzalez and Cervera and this paper, open up the possibility of using MPEG-compression at high bitrates to store or transmit high-quality speech recordings, without altering their acoustic properties.     

Regularization of Discrete Ill-Posed Problems

The paper concerns conditioning aspects of finite-dimensional problems arising when the Tikhonov regularization is applied to discrete ill-posed problems. A relation between the regularization parameter and the sensitivity of the regularized solution is investigated. The main conclusion is that the condition number can be decreased only to the square root of that for the nonregularized problem. The convergence of solutions of regularized discrete problems to the exact generalized solution is analyzed just in the case when the regularization corresponds to the minimal condition number. The convergence theorem is proved under the assumption of the suitable relation between the discretization level and the data error. As an example the method of truncated singular value decomposition with regularization is considered. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.