Isomeric states in 214Th and 213Th

Isomeric states in ²¹⁴Th and ²¹³Th were identified by means of γ -rays measured in delayed coincidence with the implanted evaporation residues. These were produced in irradiations of ¹⁶⁴Dy with ⁵⁴Cr projectiles and separated in-flight by the velocity filter SHIP. An isomeric state of I ^π = 8⁺ with a half-life of (1.24±0.12) μs was identified in ²¹⁴Th . The configuration π[1h _9/2 ⊗ 2f _7/2] was assigned to this state. An isomeric state with a half-life of (1.4±0.4) μs was observed in ²¹³Th . Tentatively it was assigned to an I ^π = 13/2⁺ state.     

p-type porous-silicon transducer for cation detection: effect of the porosity, pore morphology, temperature and ion valency on the sensor response and generalisation of the Nernst equation

This paper shows the possibility of using oxidised porous silicon (PS) as a transducer material for ion-sensor applications. It aims to study the over-Nernstian behaviour of the porous electrodes towards the concentration of cations in contact. The dependence of the sensitivity on the porosity of the samples prepared from highly doped substrates has been studied. Maximal values of over-Nernstian sensitivities around 240 mV/pNa and ∼92 mV/pCu, corresponding to a PS-layer porosity of about 65%, obtained respectively from p⁻ and p⁺ silicon substrates, have been registered. Furthermore, the effect of the porous nanostructure morphology has been studied, by preparing PS samples from weakly doped wafers. The porous-silicon-based sensor behaviour for different PS-layer thicknesses has also been experimentally investigated. According to these results, a physical model has been proposed to explain the mechanisms which govern the charge-carrier transfer from one side to the other of the functionalised oxide layer, and leads to the over-Nernstian adsorption of the cationic species at the electrolyte/SiO₂ interface. Afterwards, the Nernst relation has been generalised accordingly, on one hand, to the previous experimental results, and on the other hand, to the results obtained about the ion-valency and the electrolyte-temperature effects on the sensor responses. Received: 15 December 2000 / Accepted: 18 December 2000 / Published online: 23 March 2001     

Theory for migration of ions in capillary electrochromatography

The fundamental migration theories for chromatography and electrophoresis are both based on a solution of the mass balance equation. The corresponding analysis for an electrochromatographic system has previously been published and is analysed in more detail in this paper. It is shown that the resulting equation, Eq. (8) in this paper, is in agreement with both electrophoretic and chromatographic theories and that when these migration modes are mixed a complicated migration behaviour emerge. These complications arise, if the comparison is done with electrophoretic theory, because the presence of the stationary phase creates a number of new restrictions on the system (electroneutrality on the stationary phase and simultaneous equilibrium for all components between the eluent and stationary phase). From a mathematical point of view, these restrictions make it difficult for the system to satisfy the coherence condition and this in turn may lead to an anomalous behaviour. To minimise the possibility for a complicated behaviour it is advisable to avoid too much mixing of the two migration mechanisms and/or to match the mobilities of the ionic components in the eluent phase with the mobility of the analyte ion.     

A new method for the accurate determination of the isotopic state of single amide hydrogens within peptides using Fourier transform ion cyclotron resonance mass spectrometry

A new method is presented to accurately determine the probability of having a deuterium or hydrogen atom on a specific amide position within a peptide after deuterium/hydrogen (D/H) exchange in solution. Amide hydrogen exchange has been proven to be a sensitive probe for studying protein structures and structural dynamics. At the same time, mass spectrometry in combination with physical fragmentation methods is commonly used to sequence proteins based on an amino acid residue specific mass analysis. In the present study it is demonstrated that the isotopic patterns of a series of peptide fragment ions obtained with capillary-skimmer dissociation, as observed with a 9.4 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer, can be used to calculate the isotopic state of specific amide hydrogens. This calculation is based on the experimentally observed isotopic patterns of two consecutive fragments and on the isotopic binomial distributions of the atoms in the residue constituting the difference between these two consecutive fragments. The applicability of the method is demonstrated by following the sequence-specific D/H exchange rate in solution of single amide hydrogens within some peptides.     

The influence of polymer molecular-weight distributions on pulsed field gradient nuclear magnetic resonance self-diffusion experiments

 The influence of polymer molecular-weight distributions on the outcome of pulsed field gradient (PFG) NMR self-diffusion experiments has been considered. The self-diffusion coefficient, D, of monodisperse poly(ethylene oxide) (PEO) polymers has been determined in order to accurately determine the scaling behavior of D both with molecular weight and concentration. In order to investigate the influence of polydispersity on the PFG NMR signal, a model system consisting of ten reasonably monodisperse PEO polymers was made, and the PFG NMR signal intensities were recorded at a low total concentration. The data were analyzed using both inverse Laplace transformation and nonlinear least-squares fitting to a prescribed distribution function of D. Finally, the molecular-weight distribution was obtained by use of the values of the scaling parameters. We also present some model calculations used to investigate the sensitivity of the degree of polydispersity on the NMR signal decays. Received: 27 May 1999 Accepted in revised form: 19 October 1999     

Thermal Oxidative Stability of Heat-Stabilised Polyamide 66 by Differential Scanning Calorimetry

The thermal stability of heat-stabilised polyamide 66 in an oxidative environment is evaluated by DSC. The oxidative stability of the polyamide decreases as a result of repeated injection moulding. The results also indicate that the presence of glass fibres in the polyamide has a negative influence on the oxidative stability. Both isothermal and dynamic DSC measurements seem to be useful tools for assessing the stability of polyamides and there is a relationship between data determined using both procedures. This revised version was published online in July 2006 with corrections to the Cover Date.     

Double cyclisation of phenylglycine-o-carboxylic acids—I: New stable mesoionic oxazolones

Remarkably stable mesoionic oxazolones possessing an oxazolo[3,2-a]quinolinium structure (5a–b),8,16, 17) were obtained by the double cyclisation of phenylglycine-o-carboxylic acids (3a–c) in refluxing acetic anhydride or in benzoic anhydride at 140°, The 0-Ac group was eliminated to give the corresponding lactones (6a–b) or replaced by O-Ts (7). IR stretching vibrations of the endo-carbonyl were in the range 1710–1768 cm^?1, while v_1-CH exhibited unusually high values (3159–3194 cm^-1). 1-Acyl derivatives could be obtained only with TFAA (23–24), although easy deuteration of the same position took place in the presence of traces of trifluoroacetic acid. Hydrolysis of 5b led to the α-quinolone-N-acetic acid 27a. In the case of 5a, hydrolysis was accompanied by self-acylation of the nucleophilic site at C-4 with formation of a dimeric acid 28a. The presence of an additional Me group in phenylalanine-o-carboxylic acid (36) activates the corresponding mesoionic oxazolone 37 so that 1-acylation becomes possible with formation of the fused oxazole 38 by the Dakin-West reaction. Temperature dependent magnetic non-equivalence of methylene protons has been observed in acids 3b-d and f and also in the 7-membered anhydride 48b.     

Protein kinase A type I activates a CRE-element more efficiently than protein kinase A type II regardless of C subunit isoform

Background  

Protein kinase A type I (PKAI) and PKAII are expressed in most of the eukaryotic cells examined. PKA is a major receptor for cAMP and specificity is achieved partly through tissue-dependent expression and subcellular localization of subunits with different biochemical properties. In addition posttranslational modifications help fine tune PKA activity, distribution and interaction in the cell. In spite of this the functional significance of two forms of PKA in one cell has not been fully determined. Here we have tested the ability of PKAI and PKAII formed by expression of the regulatory (R) subunits RIα or RIIα in conjunction with Cα1 or Cβ2 to activate a co-transfected luciferace reporter gene, controlled by the cyclic AMP responsive element-binding protein (CREB) in vivo.