Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations

In order to investigate the relative effects of the differences between the structures and lipophilicities of 1, 10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TA-18-crown-6) and the tetrabenzyl derivative of 1,10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TBTA-18-crown-6) on their extraction-abilities and -selectivities for transition metal cations, constants of the overall extraction (logK _ex) of 1:1 (M:L) complexes, the distribution (K _D) for two diluents (CH₂Cl₂ and CHCl₃) with different dielectric constants have been determined at 25 ± 0.1 °C. The magnitude of logK _ex is largely determined by that of K _D. The equilibrium constants of TA-18-crown-6 have been compared with those of TBTA-18-crown-6. It is found that:(i) logK _ex sequences of TA-18-crown-6 and TBTA-18-crown-6 for transition metals in CH₂Cl₂ lie in order: Fe³⁺ > Cu²⁺ > Mn²⁺ > Co²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺ and Fe³⁺ > Cu²⁺ > Co²⁺ > Mn²⁺ > Ni²⁺ > Cd²⁺ > Zn²⁺ respectively; (ii) the stability sequences of two types of tetra-aza-crown ethers with the transition metal cations in CHCl₃ are the same as follows: Fe³⁺ > Ni²⁺ > Cu²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > Mn²⁺, and (iii) unusual selectivities are observed for transition metal-tetra-aza-crowns, e.g. the high Fe³⁺/M ⁿ⁺ selectivity factors (S_f) of TA-18-crown-6, except for the competitive-extractions for the special case in CHCl₃ of TBTA-18-crown-6, it was found that the Mn²⁺/M ⁿ⁺ values were relatively higher according to the other transition metal cations. A systematic sequence in these two types of solvents is not found for a given transition metal cation in terms of the variation of selectivity with the tetra-aza-crown ethers. The results provide alternatives for the rational design of other specific ligands on the transition metal cations.     

Laser systems specialized for laser spectroscopy at storage rings

Laser spectroscopy at storage rings often suffers from a limited resolution due to Doppler-broadened resonances. Broadening is caused by the velocity spread of the ions stored in the beam. In the following, the present status of our work on laser systems specialized on the specific needs of laser spectroscopy at storage rings is reported. Two pulsed laser systems were developed. One is a dye laser whose spectral bandwidth can be switched by inserting different Littrow-prisms into the resonator. An increase in bandwidth up to a factor of 45 was achieved. This laser was used for fast qualitative scans and high resolution measurements. The other laser system is a Nd : YAG laser pumped optical parametric oscillator. It is a tunable laser system covering the spectral range from 410 to 4000 nm. Furthermore, a continuous wave laser with a frequency shifted feedback cavity is described. It shows broadband emission with an adjustable bandwidth of up to 4.5 GHz. This laser can be advantageous for laser cooling of ion beams. This revised version was published online in August 2006 with corrections to the Cover Date.     

Symmetries of Itô and Stratonovich Dynamical Systems and Their Conserved Quantities

A new definition for the symmetries of Itô and Stratonovich dynamicalsystem is given. Determining systems of symmetries for Itô andStratonovich systems have been obtained, and their relation has beendiscussed. It has been shown that some of the Lie point symmetries ofthe Fokker–Planck equation can be constructed using the symmetries ofItô dynamical systems. Conserved quantities can be found from thesymmetries of stochastic dynamical systems which do not arise from aHamiltonian. The results have been applied to an example.     

Active Q-switching of the Alexandrite laser

An alexandrite-laser rod was actively Q-switched in the transversal fundamental mode at λ = 758 nm with an double crystal KD^*P Pockels cell. Pulse width, pulse energy and optical pulse delay (the build-up time of the photon field in the resonator) were measured as functions of pumping energy, rod temperature and reflectivity of the output coupling mirror. As the laser gain of alexandrite strongly depends on temperature, the pulse width and pulse energy were also investigated as functions of the temperature of the active material. A comparison of experimental data with theory was made.     

Eigenvalues of Two Parameter Polynomial Operator Pencils of Waveguide Type

The spectral structure of two parameter unbounded operator pencils of waveguide type is studied. Theorems on discreteness of the spectrum for a fixed parameter are proved. Variational principles for real eigenvalues in some parts of the root zones are established. In the case of n = 1 (quadratic pencils) domains containing the spectrum are described (see Fig. 1–3). Conditions in the definition of the pencils of waveguide type arise naturally from physical problems and each of them has a physical meaning. In particular a connection between the energetic stability condition and a perturbation problem for the coefficients is given.     

Über die Stromdichtepotentialkurven passivierbarer Metalle,am Beispiel des Eisens dargestellt

Zusammenfassung Es wurde an Hand des Zahlenmaterials meiner Arbeit »Über die Passivierung speziell des Eisens« a. a. O. gezeigt, da\ man unter BerÜcksichtigung der Zeiterscheinungen Stromspannungskurven fÜr die Passivierung des Eisens erhält, welche aus zwei ästen bestehen. Von diesen entspricht der eine dem Verhalten des aktiven, der andere dem Verhalten des passiven Metalles. Die frÜheren, ohne BerÜcksichtigung der Zeitverhältnisse von verschiedenen Forschern aufgestellten Kurven entsprechen mehr oder weniger Zufallswerten, geben das Verhalten eines Metalles, das aktiv und passiv auftreten kann, nicht vollständig wieder und sind als Grundlage theoretischer Diskussionen unzureichend.     

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Ohne Zusammenfassung     

An oestrogen-derivative labeled with 99mTc and its radiopharmaceutical potential

An oestrogen derivative 3,17-a-oestradiolyl propyl 1,4,8,11-tetraazacyclotetradecanyl-1-(4-methylbenzoic acid)ester (ESTCPTA) that is 3,17-a-oestradiolyl propinol coupled to 1-(4-methylbenzoic acid)1,4,8,11-tetraazacyclotetradecane (CPTA) was synthesized in five steps. The product was purified by recrystallization in ethyl alcohol, and analysed by NMR and IR spectroscopy. ESTCPTA was labeled with ^99mTc and radio thin layer chromatography (RTLC) and radio-paper electrophoresis were used to determine the radiochemical yields. Specific activity was approximately 23.7 GBq/mmol and the labeling yield was over 95%. The biodistribution studies were performed on female Albino Wistar rats. The rats were sacricified by ether narcotization at certain time intervals and the activity of the organs was counted by a gamma counter. The activity per gram tissue was calculated and time activity curves were generated.     

Dioxomolybdenum(VI) complexes of 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone

Mixed ligand complexes of dioxomolybdenum(VI) with 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone (H₂L) were prepared with the formula [MoO₂(L)D] (D = H₂O, methyl, n-butyl, and n-undecyl alcohol, DMF, DMSO, pyridine, 4-picoline, and 3,5-lutidine). The compounds were characterized by elemental analysis, IR and ¹H NMR spectroscopy. The thermal decomposition of the compounds were investigated by using TGA, DTG, and DTA methods in air, and the thermal behavior depending on the second ligand molecule was discussed. A single crystal of the DMF coordinated complex was studied by X-ray diffractometry. The text was submitted by the authors in English.