Solubilizing sodium fluoride in acetonitrile: synthesis, molecular structure, and complexation behavior of bis(organostannyl)methyl-substituted crown ethers

The synthesis of the crown-ether-substituted bis(organostannyl)methanes Ph(3)SnCH(2)Sn(Ph(2))-CH(2)-[16]crown-5 (1) and Ph(2)ISnCH(2)Sn(I)(Ph)-CH(2)-[16]crown-5 (2) is reported. Both compounds have been characterized by elemental analyses, (1)H, (13)C, (19)F, and (119)Sn NMR spectroscopy, and in the case of compound 2 also by electrospray ionization mass spectrometry. Single-crystal X-ray diffraction analysis revealed for the aqua complex 2.H(2)O trigonal-bipyramidal-configured tin atoms with intramolecular Sn(1)-O(1) and Sn(2)-O(1W) distances of 2.555(2) and 2.440(3) A, respectively. The water molecule is trapped in a sandwich-like fashion between the crown ether oxygen atoms O(2) and O(4) and the Sn(2) atom. NMR spectroscopy unambiguously proved the ability of compound 2 in acetonitrile to overcome the high lattice energy of sodium fluoride and to complex the latter under charge separation.     

Tetranuclear BINOL-titanium complex in selective direct aldol additions

The extremely robust and water-stable tetranuclear complex Ti(4)(micro-BINOLato)(6)(micro(3)-OH)(4) (1) catalyzes the direct aldol addition with high degrees of regioselectivity at the sterically more encumbered alpha-side of unsymmetrical ketones. The formation of quaternary stereocenters is described. Oxygen-containing ene components can also be used as starting material in these reactions. When used with aliphatic aldehydes, acetals 18 or acetals of aldol adducts 20 were observed. As few as 0.2 mol % loadings with this catalyst 1 were enough to complete the reactions. Mechanistical aspects of the reactions are discussed.     

Detecting proximities between quadrupolar nuclei by double-quantum NMR

A robust, easy to optimize, and efficient homonuclear correlation NMR experiment for half-integer quadrupolar nuclei in solids is described and has been experimentally tested on anhydrous Na2HPO4-(23Na, S= 3/2 nucleus) and as-synthesized AlPO4-14 (27Al, S= 5/2 nucleus), an aluminophosphate molecular sieve.     

Flexibility of phenylene oligomers revealed by single molecule spectroscopy

The rigidity of a p-phenylene oligomer (p-terphenyl) has been investigated by single molecule confocal fluorescence microscopy. Two different rylene diimide dyes attached to the terminal positions of the oligomer allowed for wavelength selective excitation of the two chromophores. In combination with polarization modulation the spatial orientation of the transition dipoles of both end groups could be determined independently. We have analyzed 597 single molecules in two different polymer hosts, polymethylmethacrylate and Zeonex. On average we find a 22 degrees deviation from the linear gas phase geometry (T = 0 K), indicating a rather high flexibility of the p-phenylene oligomer independent of the matrix. To substantiate our experimental results, we have performed quantum chemical calculations at the density functional theory level for the molecular geometry and the electronic excitations. Our findings are in agreement with former experiments on the persistence length of poly(p-phenylenes).     

Antioxidant properties of natural and synthetic chromanol derivatives: study by fast kinetics and electron spin resonance spectroscopy

[structure: see text] Chromanol-type compounds act as antioxidants in biological systems by reduction of oxygen-centered radicals. Their efficiency is determined by the reaction rate constants for the primary antioxidative reaction as well as for disproportionation and recycling reactions of the antioxidant-derived radicals. We studied the reaction kinetics of three novel chromanols: cis- and trans-oxachromanol and the dimeric twin-chromanol, as well as ubichromanol and ubichromenol, in comparison to alpha-tocopherol and pentamethylchromanol. The antioxidant-derived radicals were identified by optical and electron spin resonance spectroscopy (ESR). The kinetics of the primary antioxidative reaction and the disproportionation of the chromanoxyl radicals were assessed by stopped-flow photometry in different organic solvents to simulate the different polarities associated with biomembranes. Furthermore, the reduction of the chromanoxyl radicals by ubiquinol and ascorbate was measured after laser-induced one-electron chromanol oxidation in ethanol and in a micellar system, respectively. The rate constants showed that twin-chromanol had better radical scavenging properties than alpha-tocopherol and a significantly slower disproportionation rate of its corresponding chromanoxyl radical. In addition, the radical derived from twin-chromanol is reduced by ubiquinol and ascorbate at a faster rate than the tocopheroxyl radical. Finally, twin-chromanol can deliver twice as many reducing equivalents, which makes this compound a promising new candidate as artificial antioxidant in biological systems.     

Spin-locking and recoupling of homonuclear dipolar interaction between spin-3/2 nuclei under magic-angle sample spinning

Numerical simulations and experiments were used to examine the possibility of employing strong spin-lock fields for recoupling of homonuclear dipolar interactions between spin-3/2 quadrupolar nuclei and to compare it to the rotary-resonance recoupling at weak spin-lock fields. It was shown that strong spin-lock pulses under MAS conditions can lead to recoupling, provided that the electric-field gradient principal axes systems of the coupled nuclei are aligned and that their quadrupolar coupling constants are approximately the same. The phenomenon is based on the fact that strong spin-lock pulses induce adiabatic transfer of magnetization between the central-transition coherence and the triple-quantum coherence with equal periodicity as is the periodicity of the time-dependent dipolar coupling. Because of the synchronous variation of the state of the spin system and of the dipolar interaction, the effect of the latter on the central-transition coherence and on the triple-quantum coherence is not averaged out by sample rotation. The approach is, however, very sensitive to the relative orientation of the electric-field gradient principal axes systems and therefore less robust than the approach based on weak spin-lock pulses that satisfy rotary-resonance condition.     

Experimental two-photon,three-dimensional entanglement for quantum communication

Orbital angular momentum entangled photons emitted by a down-conversion source are in higher dimensional entangled states. Here we report the experimental confirmation by demonstrating a violation of a generalized Clauser-Horne-Shimony-Holt-type Bell inequality in three dimensions by more than 18 standard deviations. Higher dimensional entangled states allow the realization of new types of quantum communication protocols. They also provide a more secure quantum cryptography scheme. Therefore our experimental results are likely to have applications in future quantum communication technology.     

Detection limits and surface interactions in quantitative negative chemical-ionization mass spectrometry Ultratrace determination of metals and organic compounds by means of their complexes

Details are given of a selective negative-ion mass-spectrometric method appropriate for the ultratrace determination of metals and organic compounds by means of their complexes. Direct introduction of the sample into the ion-source, attachment of low-energy electrons, and selected-ion monitoring are described, and comparative data are given relating to surface effects at the tips of insertion-probes on detection limits. Detection limits for chromium and cobalt, determined as their tris(2,2,6,6-tetramethylheptane-3,5-dione) chelates, were respectively 1.0 and 0.16 pg, and that for nickel [as its bis(N,N-diethyldithiocarbamate) complex] was 1.0 pg. Detection limits of 2.0 and 1.0 ng are attainable for malathion and ethion by measurement of the nickel(II) complexes of their O,O'-dialkyldithiophosphate hydrolysis products.     

Über das Randverhalten der Bergmanschen Kernfunktion und Metrik für eine spezielle Klasse schwach pseudokonvexer Gebiete des ℂ n

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