Characterization of amino acid‐derived betaines by electrospray ionization tandem mass spectrometry

Betaines belong to the naturally occurring osmoprotectants or compatible solutes present in a variety of plants, animals and microorganisms. In recent years, metabolomic techniques have been emerging as a fundamental tool for biologists because the constellation of these molecules and their relative proportions provide with information about the actual biochemical condition of a biological system. Therefore, identification and characterization of biologically important betaines are crucial, especially for metabolomic studies. Most of the natural betaines are derived from amino acids and related homologues. Although, theoretically, all the amino acids can be converted to corresponding betaines by simple methylation of the amine group, only a few of the amino acid‐derived betaines were fully characterized in the literature. Here, we report a combined electrospray ionization tandem and high‐resolution mass spectrometry study of all the betaines derived from amino acids, including the isomeric betaines. The decomposition pathway of protonated, sodiated and potassiated molecule ions that enable unambiguous characterization of the betaines including the isomeric betaines and overlapping ionic species of different betaines is distinctive. Copyright © 2012 John Wiley & Sons, Ltd.     

Influence of the crystallite size on the phase transformation of yttria irradiated with swift heavy ions

The irradiation effects induced by swift heavy ions are now widely described in `bulk' materials. It is shown here that the behaviour of matter under irradiation depends on its crystalline state in the sense that a given material is all the more sensitive to swift heavy ion irradiations as the mean crystallite size L is small. The present paper relates the experimental results obtained in yttrium oxide from `in situ' X-ray diffraction measurements. Three kinds of sample have been irradiated: sintered samples (L = 1μm), non-ground powders (L = 45 nm) and ground powders (L = 28 nm). A cubic to monoclinic phase transformation appears if the electronic energy loss of the incident particle is higher than a threshold. The comparison between the different kinds of samples reveals that this phase transformation is all the easier as the mean crystallite size of the target is weak. Received 27 January 2000 and Received in final form 13 December 2000     

Excitation of isomeric 1h 11/2 states in nuclear reactions induced by γ rays and neutrons and in beta decay

Isomeric ratios were measured for N=81 isotones (¹³⁵Xe, ¹³⁷Ba, ¹³⁹Ce, ¹⁴¹Nd, ¹⁴³Sm). In the experiment reported here, μ _ν ≤3±10^? J ^π=11/2^? isomers were excited in (n, γ) and (γ, n) reactions and in the β ⁺ decay of ¹³⁹Pr and ¹⁴¹Pm. In order to determine the reaction yields, use was made of the activation method involving measurement of the gamma-ray spectra of reaction products. It is found that, in the same reactions, isomeric ratios are different for isotones characterized by different atomic numbers Z. Isomeric ratios were calculated with the spectra of low-lying levels and radiative-transition probabilities established on the basis of the quasiparticle-phonon model. Good agreement between the experimental and calculated values of isomeric ratios is obtained for all isotopes invesigated here. The dependence of isomeric ratios on the atomic number Z of a nucleus is explained by the difference of reaction energies, which leads to different probabilities of excitation of activation levels through which the isomers being considered are populated.     

Influence of Residual Polyesterification Catalysts on the Curing of Polyesters

 Unsaturated polyesters are synthesized by means of polyesterification, often with catalysts like strong acids, metal oxides and metal-organic salts. Most often, the catalysts used cannot be separated from the bulk of the polyester. Also, some organic or inorganic additives – called fillers – which are used with the polyester in order to decrease cost, affect the curing of the polyester. In this work the effect of residual catalyst on the curing of unsaturated polyester is studied. Unsaturated polyesters were prepared using propylene glycol with a 10% molar excess over stoichiometry and a mixture of dicarboxylic acids, namely maleic acid (unsaturated) adipic acid (saturated) and phthalic anhydride (saturated) at a molar ratio 1:2:2. Lead dioxide, p-toluenesulfonic acid and zinc acetate were used as catalysts, at 0.1% w/w. After the polyesterification, the polymers were diluted with styrene at a proportion of 100:30 w/w. The resins were cured by using MEKP (methylethylketone peroxide) as initiator and CoNp (cobalt naphthenate) as accelerator. Catalysts affect the final color of the polyester. The kinetics of curing of the resins was studied by DSC analysis based on the exothermic peak due to the double bonds breaking to give crosslinked macromolecules. The heat released ΔH is decreased by the presence of catalyst, while activation energy, the frequency factor and the order of reaction are increased.     

Vibrational circular dichroism: a new spectroscopic tool for biomolecular structural determination

Vibrational circular dichroism (VCD) in the past two decades has developed into a powerful new structural tool. A concise review of the applications of VCD to determine the structures of various biological molecules, namely peptides and proteins, nucleic acids and carbohydrates, is provided. Received: 31 August 1999 / Revised: 2 November 1999 / Accepted: 14 November 1999     

Thickness shear mode resonators (“mass-sensitive devices”) in bioanalysis

A short overview of function and experimental set-ups of acoustic wave devices is given which, in contrast to other bioanalysis techniques, are based on a mechanical transduction mechanism. The most frequently used device is the thickness shear mode resonator (TSMR), which in the last few years was intensively employed in biosensor applications. TSMR biosensor studies in the field of nucleic acid interaction, adsorption of proteins to surfaces and immunosensing are reviewed. A main point concerns the interpretation of the sensor response not only in terms of mass loading, which underestimates the capabilities of these devices.     

Formation and dissolution of InAs quantum dots on GaAs

In situ reflection high energy electron diffraction (RHEED) has been used to study the time evolution during self-assembled molecular beam epitaxy (MBE) growth of InAs quantum dots on GaAs. Using a special data acquisition technique, two characteristic time constants are determined very precisely: the time t_c up to the first appearance of InAs dots and the time t_f it takes to complete the 2D–3D transition of all islands. Surprisingly, we find that t_c increases with temperature which disagrees with a thermally activated process. In contrast to this, t_f behaves Arrhenius-like and an activation energy of E_f0.39 eV is determined. Furthermore, the sum t_c+t_f does not depend significantly on temperature and corresponds to an InAs coverage of 2.0 monolayers. A second focus of this paper is the study of dissolution of InAs dots after interruption of the As flux. From the experiments, an activation energy of 3.2 eV for desorption of In located on top of the wetting layer is determined, whereas direct desorption from the wetting layer corresponds to an activation energy of 3.4 eV.     

The AURORA Financial Management System: Model and Parallel Implementation Design

The AURORA financial management system under development at the University of Vienna is a modular decision support tool for portfolio and asset–liability management. It is based on a multivariate Markovian birth-and-death factor model for the economic environment, a pricing model for the financial instruments and an objective function which is flexible enough to express risk aversion.The core of the system is a large scale linear or convex program, which due to its size and structure is well suited for parallel optimization methods.As the system is still at an early stage of development, the results are preliminary in nature. Only a few types of financial instruments are handled and just two types of objectives are considered. The parallel optimization modules are still in the development phase.     

Scenario tree generation for multiperiod financial optimization by optimal discretization

Multiperiod financial optimization is usually based on a stochastic model for the possible market situations. There is a rich literature about modeling and estimation of continuous-state financial processes, but little attention has been paid how to approximate such a process by a discrete-state scenario process and how to measure the pertaining approximation error.?In this paper we show how a scenario tree may be constructed in an optimal manner on the basis of a simulation model of the underlying financial process by using a stochastic approximation technique. Consistency relations for the tree may also be taken into account. Received: December 15, 1998 / Accepted: October 1, 2000?Published online December 15, 2000