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.     

The critical exponent of degenerate parabolic systems

The Cauchy problemu _t=u +v ^p ,v _t =v +u ^q is studied, wherex R ^N , 0 <t < and ,,p andq, are positive exponents. It is proved that ifp,q 1 and 1 <pq < 1 + 2 max(p + ,q + )/n then every nontrivial non-negative solution is not global in time; whereaspq > 1 + 2 max(p + , q + )/n then there exist both positive global solutions and non-global solutions. In addition, the decaying in time of solutions tou _t,=u inR ⁿ × (0, ), an equation which occurs naturally in our study of above systems, is studied and solutions with the fastest decaying in time are constructed.     

Dearomatising rearrangements of lithiated thiophenecarboxamides

Thiophene-3-carboxamides bearing allyl or benzyl substituents at nitrogen undergo dearomatising cyclisation on treatment with LDA. Rearrangements transform the dearomatised products into pyrrolinones, azepinones or partially saturated azepinothiophenes.     

Sulfoxides as ‘traceless’ resolving agents for the synthesis of atropisomers by dynamic or classical resolution

Reacting (−)-menthyl sulfinate with an atropisomeric but racemic aryllithium gives two atropdiastereoisomeric sulfoxides. Separation (by chromatography or crystallisation) and sulfoxide-lithium exchange of each diastereoisomer regenerates the aryllithium in enantiomerically pure form which can be quenched with a range of electrophiles with retention of stereochemical integrity. Overall the reaction sequence is a resolution but without the need for an acidic or basic substituent—a ‘traceless’ method. In certain instances, for example when the nucleophile is an ortholithiated peri-substituted 1-naphthamide, the diastereoisomeric sulfoxides may be interconverted thermally. This allows a dynamic resolution, under thermodynamic control, and hence in principle can give yields of the final products of greater than 50%. The utility of the method is demonstrated by the synthesis of a known atropisomeric phosphine ligand.     

Synthesis, crystal structure, and nonlinear optical behavior of beta-unsubstituted meso-meso E-vinylene-linked porphyrin dimers

[structure: see text] A vinylene-linked porphyrin dimer, with no substituents at the beta-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the crystal structure of this dimer, the C(2)H(2) bridge is twisted by 45 degrees relative to the plane of the porphyrins. The absorption, emission spectra, and electrochemistry reveal substantial porphyrin-porphyrin pi-conjugation. The triplet excited-state absorption spectrum of this dimer makes it suitable for reverse saturable absorption at 710-900 nm.     

Nuclear magnetic resonance chemical shift of the water proton in aqueous tetrabutylammonium butyrate solutions

Water proton chemical shifts have been measured for aqueous solutions of tetrabutylammonium butyrate and tetrabutylammonium bromide as a function of salt concentration and temperature. Large, negative (downfield) salt shifts are reported for Bu₄NBut solutions at temperatures below 33°C. The chemical shift becomes more negative with increasing molality up to about 0.5 m: at higher compositions, the chemical shift levels or becomes less negative. These results suggest that hydrophobic hydration cages formed under the influence of Bu₄NBut have their maximum size at approximately 0.5 m and that at higher concentrations overlap of these cages must occur as suggested by earlier thermodynamic investigations. The observed downfield molal chemical shifts are much larger than those estimated from individual ionic contributions, suggesting a mutual enhancement or linking together of hydration cages even in dilute solution.