Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

Ueber Sulfos?uren in Harn

Ohne Zusammenfassung     

Projektive Punktskalen und Summationsformeln für Tschebyscheff-Polynome

Zusammenfassung. Mit Hilfe der projektiven Geometrie werden neuartige Summationsformeln hergeleitet, die die Tschebyscheff-Polynome und modifizierte Polynome enthalten; z. B. gilt für alle : Daraus ergeben sich wiederum interessante Summationsformeln für die Hyperbelfunktionen; es gilt z. B. für positive reelle Zahlen t: Eingegangen am 28.02.96, revidierte Fassung am 25.08.97 / Angenommen am 09.10.97     

Comparative study of the cope rearrangement of hexa-1,5-diene and barbaralane

The classical rules for Cope rearrangements predict a transition state with chair form to be favored over the boat form. On the other hand, bridged homotropylidenes, which allow only a boat-form transition state by steric reasons, have extremely low barriers. A controversy about the correct pathway and the different possible intermediates and transition states of the reaction has gone on for years. In this work, the hypersurfaces of barbaralane, in comparison with the boat- and chair-form of hexa-1,5-diene, are computed by the ab inito CASSCF (6,6)/6-31G** method starting with UMP2/6-31G** natural orbitals (NO's). All three hypersurfaces show characteristic features, and, moreover differ from each other. A hitherto undiscussed intermediate, bicyclo[2.2.0]hexane, was localized on the boat-hexa-1,5-diene pathway. So it is noteworthy that our transition state for the boat-hexa-1,5-diene does not correspond to the transition states found by other authors for this conformation. The computed enthalpies of activation of boat- and chair-hexa-1,5-diene, and barbaralane are in good agreement with the experimental data.     

THE ENERGY ASPECT OF THE RECIPROCAL INTERACTIONS OF PAIRS OF TWO DIFFERENT VIBRATION MODES OF A CLAMPED ANNULAR PLATE

The standardized mutual active and reactive sound power of a clamped plate, representing the energy aspect of the reciprocal interactions of two different in vacuo modes, has been computed. It was assumed that the vibrations are axisymmetric, elastic and time harmonic, the plate's transverse deflection is small as compared with the plate's size, and that the vibration velocity is small as compared with the acoustic wavenumber generated. The Kirchhoff-Love theory of a perfectly elastic plate was used. The integral formulae for the mutual sound power were transformed into their Hankel representations which made possible their subsequent computation. A closed path integral was used to express the integral in its Hankel representation to compute the mutual active sound power. The asymptotic stationary phase method was used to compute the two magnitudes, i.e., the mutual active and reactive sound power. The results obtained are the asymptotic formulae valid for the acoustically fast waves. The oscillating as well as the non-oscillating terms have been identified in the formulae to make possible their further separate analysis. The availability of the asymptotic formulae makes possible some fast numerical computations of the mutual sound power. Moreover, the formulae presented herein, together with those for the individual modes known from the literature, make a complete basis for further computations of the total sound power of the plate's damped and forced vibrations in fluid.     

Luminescence kinetic and association equilibria of lanthanide ions in aqueous solutions. II. Determination of the formation constant of Tb acetato complex by means of luminescence lifetime measurement

The association constant K of mono-acetato complex of Tb³⁺ has been determined at normal p and T conditions by measurement of its luminescence lifetime in aqueous solution containing increasing concentrations of acetate. Two experimental arrangements used for the measurement are described.     

Die Mikrobestimmung der Fettsäuren im Blutserum

Analytical and Bioanalytical Chemistry -