On the interpretation of fluorescence anisotropy decays from probe molecules in lipid vesicle systems

Measurements of fluorescence depolarization decays are widely used to obtain information about the molecular order and rotational dynamics of fluorescent probe molecules in membrane systems. This information is obtained by least-squares fits of the experimental data to the predictions of physical models for motion. Here we present a critical review of the ways and means of the data analysis and address the question how and why totally different models such as Brownian rotational diffusion and wobble-in-cone provide such convincing fits to the fluorescence anistropy decay curves. We show that while these models are useful for investigating the general trends in the behavior of the probe molecules, they fail to describe the underlying motional processes. We propose to remedy this situation with a model in which the probe molecules undergo fast, though restricted local motions within a slowly rotating cage in the lipid bilayer structure. The cage may be envisaged as a free volume cavity between the lipid molecules, so that its position and orientation change with the internal conformational motions of the lipid chains. This approach may be considered to be a synthesis of the wobble-in-cone and Brownian rotational diffusion models. Importantly, this compound motion model appears to provide a consistent picture of fluorescent probe behavior in both oriented lipid bilayers and lipid vesicle systems.     

An efficient synthesis of [1,1]ferrocenophane via 1,1′-bis(6-fulvenyl)ferrocene

[1,1]Ferrocenophane can be prepared by reduction of 1,1′-bis(6-fulvenyl)ferrocene with complex borohydrides to give the dianion of 1,1′-bis(cyclopentadienylmethyl)ferrocene. Reaction of this dianion with ferrous chloride produces the ferrocenophane in good yield.     

Benzo[b]thiophene as a template for substituted quinolines and tetrahydroquinolines

An original methodology starting from 3-aroyl-2-(2′-nitro-4′-methoxyphenyl)-benzo[b]thiophene allows the synthesis of unusual fused heterocycles. Direct hydrogenation with nickel catalysts followed by desulfurisation led to 2,3-diarylquinolines or 2,3-diaryltetrahydroquinolines.     

Two-electron-transfer redox systems,part 7: two-step electrochemical oxidation of the boron subhalide cluster dianions B6X 2- 6 (X = Cl,Br, I)

Boron subhalide cluster dianions B6X 2- 6 (X = Cl, Br, I) are electrochemically oxidized in two steps. According to cyclic voltammograms, the first step is chemically reversible and yields the corresponding radical anions B6X .- 6. The electron transfer is nearly diffusion controlled. The second, slower electron-transfer step leads to a species which we assume to be the hitherto not yet described neutral compounds B6X 2- 6. The voltammograms indicate a coupled fast catalytic reaction, producing the radical anions in a reduction by an electrolyte component. Computer simulations of the cyclic voltammograms reveal mechanistic details of the redox reactions, as well as quantitative values for formal potentials, rate constants, and diffusion coefficients. The results are compared to other BnXn redox systems.     

Size control of dendrimer-templated silica

One of the most significant challenges facing the biomimetic synthesis of materials is achieving the requisite level of dimensional and spatial control. Typical reaction conditions for biomimetic silica synthesis allow for continued growth and ripening leading to the formation of larger nanospheres on the order of 200-600 nm in diameter. Herein, we have used polyamidoamine and polypropylenimine dendrimers as templates to expand the reaction conditions of biogenic silica production to produce a more robust synthesis leading to size-selective precipitation of silica nanospheres. Through the use of defined concentrations of phosphate buffer and main group metal chloride salts, we have shown that the biomimetic silica growth process is controlled by cationic neutralization of the anionic silica nanosphere surface. Neutralization minimizes electrostatic repulsions, allowing for agglomerization and continued growth of nanospheres. By controlling these concentrations, we can selectively produce silica nanospheres of desired dimensions between 30 and 300 nm without adversely affecting the template's activity.     

Quantitative depth profiling in glow discharge spectroscopies – A new deconvolution technique to separate effects of an uneven erosion crater shape

An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system.     

Photochemistry of condensed isoxazolines

Summary The condensed bridged isoxazolines4 are rearranged on irradiation with a low-pressure mercury lamp exclusively into condensed derivatives of tetrahydropyridine5. The selectivity of the rearrangement is due to a stabilization of the biradical8 by the overlap of the radical-electrons with -electrons of the C=C double bond and the heterocyclic ring. Quantum yields of the photorearrangement, established from the consumption of the starting materials4, were determined.

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Photochemie kondensierter Isoxazoline

Zusammenfassung Die kondensierten überbrückten Isoxazoline4 werden durch Bestrahlen mit einer Niederdruckquecksilberlampe ausschließlich zu kondensierten Tetrahydropyridinderivaten (5) umgelagert. Die Selektivität der Umlagerung beruht auf der Stabilisierung des Diradikals8 durch Überlappung der ungepaarten Elektronen mit -Elektronen der C=C-Doppelbindung und des Heterocyclus. Aus dem Verbrauch an Ausgangsmaterial (4) wurden Quantenausbeuten der Photoumlagerung bestimmt.