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.     

Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

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.     

Biosorption of Chromium(III) by Biomass of Seaweed Sargassum sp. in a Fixed-Bed Column

This work aimed at modeling chromium biosorption using the biomass of seaweed Sargassum sp. in a fixed-bed column. The mathematical model used was obtained from the mass balance of the component in the liquid phase and in the biosorbent material. The effects of both axial dispersion in the column and the resistance to mass transfer in the solid were considered for the solution of the partial differential equations of the model, using the Galerkin method on finite elements. To represent the equilibrium data of the batch system the Langmuir isotherm were used. The chromium ion adsorption capacity of the seaweed Sargassum sp., at a temperature of 30°C and pH 3.5, was 2.61 mmol/g. The model performance was evaluated from experimental data obtained at 30°C for flow rates of 2, 6 and 8 mL/min. The parameters of the model, mass transfer and axial dispersion coefficients, were adjusted from these experimental data. The model proved adequate to describe chromium biosorption dynamics in fixed-bed columns.     

Tracing Possible Structural Asymmetry of Silica Gel Used for Precoating Thin-Layer Chromatography Plates

JPC – Journal of Planar Chromatography – Modern TLC - We have previously described unexpected two-dimensionality in the thin-layer chromatographic separation of pairs of enantiomers of...     

Finitely additive integration and local integration with respect to upper integrals

Summary We study the integration theory for general integral metrics when restricted to upper integrals q, finding improvements in the relation between the classes of the q-integrable and the q_l-integrable functions. We give new results and notions which lead to the desirable characterizations of q-integrable functions as q_l-integrable f with q(|f|) < ∞, and of q_l-integrable functions via the integrability of their upper truncations, under natural conditions which are fulfilled in most finitely additive integration theories.     

Working group report: Quantum chromodynamics

This is the report of the subgroup QCD of Working Group-4 at WHEPP-9. We present the activities that had taken place in the subgroup and report some of the partial results arrived at following the discussion at the working group meetings.