Sensitive detection and separation of fluorescent derivatives using capillary electrophoresis with laser-induced fluorescence detection with 532 nm Nd:YAG laser

Capillary electrophoresis with laser-induced fluorescence detection (CELIF) is a powerful tool for separation and sensitive determination of fluorescent species. Biologically active compounds, such as amino acids, peptides and proteins may exhibit native fluorescence, which is however often low and/or an expensive laser is required for excitation in UV. Therefore, labelling of the analytes with a fluorescent dye is usually necessary.In this work, a home-built CELIF instrument with diode pumped frequency-doubled continuous wave Nd:YAG excitation laser with feedback power regulation (532 nm) was constructed. The suitability of this type of laser for LIF detection in a separation method was found excellent. A limit of detection (LOD) (S/N=3) of 2×10⁻¹³ mol/l was achieved with rhodamine B, which is comparable to those obtained using similar instruments with Ar⁺ laser [Y.F. Cheng, N.J. Dovichi, Science 242 (1988) 562, E.S. Yeung et al., J. Chromatogr. 608 (1992) 73]. LOD of a protein derivatized according to modified procedures [M.J. Little et al., Anal. Chim. Acta 339 (1997) 279, A. Chersi et al., Biochim. Biophys. Acta 1336 (1997) 83] was determined. Detection of the derivatives was found to be limited by insufficient reaction recovery at low analyte concentration, chemical noise, separation efficiency and quality of the derivatizing reagent rather than by the detector performance. As a consequence, a huge gap between the detection ability of CELIF instruments and LOD determined in real samples is revealed.     

The Aharonov–Bohm effect in graphene rings

This is a review of electronic quantum interference in mesoscopic ring structures based on graphene, with a focus on the interplay between the Aharonov–Bohm effect and the peculiar electronic and transport properties of this material. We first present an overview on recent developments of this topic, both from the experimental as well as the theoretical side. We then review our recent work on signatures of two prominent graphene-specific features in the Aharonov–Bohm conductance oscillations, namely Klein tunneling and specular Andreev reflection. We close with an assessment of experimental and theoretical development in the field and highlight open questions as well as potential directions of the developments in future work.     

Baryon production in the string fragmentation picture

An improved version of the “pop-corn” model for baryon production in quark and gluon jets is presented. With a reduced number of parameters the model reproduces well both production rates for different baryon species and baryon momentum distributions. Predictions are presented for a set of baryon-antibaryon correlations.     

An analytical and experimental comparison of optimal actuator and error sensor location for vibration attenuation

Feedforward active control of the flexural waves in a single and L-shaped plate has been analytically and experimentally investigated. The plates are simply supported along two parallel edges, and free at the other two ends. Point forces were used to generate the primary and secondary plate excitations. The plate flexural displacement is described by a combination of a travelling wave solution and a modal expansion. The flexural wave coefficients were determined using the boundary conditions, continuity equations at the driving force locations, and continuity equations at the corner junction for the L-shaped plate. The control actuator and error sensor are optimally located in order to achieve the best control performance.     

Die Reduktion von Ammoniumpolyuranat zu Urandioxid

Zusammenfassung Es werden die Resultate des isothermen Zerfalles und der Reduktion vonstandardisiertem Ammoniumpolyuranat im Bereich von 285 bis 463° C (in Wasserstoff) wiedergegeben. Der Zerfall zu UO₃ wurde schon bei einer Temp. unter 290° C festgestellt, diese Phase blieb jedoch darauf stabil bis 320° C. Zwischen 320° C und 380° C verläuft die Reduktion zu U₃O₈, über 380° C aber zu UO₂. Die Aktivierungsenergien bei der Reduktion von UO₃ zu U₃O₈ und von U₃O₈ zu UO₂ wurden berechnet, und zwar 32,2 kcal/g-mol und 41,7 kcal/g-mol. Die Ergebnisse können mit den Literaturangaben für die Reduktion der einzelnen Phasen UO₃ und U₃O₈ verglichen werden. Die beobachteten Unterschiede weisen auf den Einfluß der Aktivität der Präparate hin.

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The isothermal decomposition and reduction of ammonium polyuranate (ADU) was investigated in the temperature interval 285–463° C in hydrogen. The formation of UO₃ was noticed below 290° C and this product was stable up to 320° C. U₃O₈ was stable from this temperature on up to 380° C, where the reduction to UO₂ was observed. The activation energies 32,2 Kcal/mole and 41.7 Kcal/mole were calculated for the reduction of UO₃ to U₃O₈ and for the reduction of U₃O₈ to UO₂, respectively. The results are comparable with the published data on reduction of separate phases UO₃ and U₃O₈. Some differences noticed show the influence of the activities of the products.

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Mit 4 Abbildungen     

Heterocycles from amino acids. A novel synthetic approach for imidazo[1,5-a]pyridines and imidazo[1,5-a]quinolines

From the corresponding heterocyclic amino acids 2 and 9a the heterocyclic systems imidazo[1,5-a]pyridine ( 3 ) and imidazo[1,5-a]quinoline ( 10 ) are easily accessible. From compound 7 the tricyclic system 11 was prepared and from compound 17a a pyridyl-1,2,4-triazinone ( 18 ) could be obtained.     

Preparation of an ion-selective electrode by chemical treatment of copper wire for the measurement of copper(II) and iodide by batch and flow-injection potentiometry

The preparation of an ion-selective electrode by chemical treatment of copper wire and its application for the measurements of copper (II) and iodide ions is described. The proposed reaction mechanism at the sensing surface, which explains the response of the electrode to Cu²⁺ and iodide ions, is discussed. The prepared electrode was suitable for direct potentiometric measurements of iodide and copper (II) in batch experiments down to concentrations of 1 × 10^–5 mol L^–1. A tubular electrode, prepared in the same way, may be used as a potentiometric sensor in a flow-injection analysis for Cu (II) and/or iodide determinations.     

POLARIZED FLUORESCENCE OF 5-METHYLCYTOSINE SPECIES IN SOLUTION AT ROOM TEMPERATURE

Fluorescence yields (π_f,'s) and polarizations ( P ) are measured for aqueous 5-methylcytosine (˜ 0.1 m M ) at 20°C as a function of pH over the range 2–14. Both properties change abruptly and in parallel at pH's corresponding to the known pK_a values. Polarizations were also obtained for the 5-methylcytosine cation, neutral and anion species in ethylene glycol water glass at ˜180K. The weak fluorescence of the neutral and cation species at 20°C was polarized almost as highly as at low temperature. When the fluorescence lifetimes are assumed to be correctly given by the product of calculated radiative lifetimes and quantum yields, the polarizations are found to be consistent with rotational diffusion rates ˜4 times faster than predicted from Stokes-Einstein models for the neutral and anion species. The cation seemed to rotate about two times more slowly than the neutral and anion species. It was also shown that the properties of the three species are such that a plot of 1/P vs apparent π_f in the pH range 2–11 is fortuitously linear.