Bacteriorhodopsin as an Example of a Light-Driven Proton Pump

Apart from the long known visual pigments, another retinal protein complex exists in nature, viz. bacteriorhodopsin from halobacteria. In contrast to the visual pigments such as the rhodopsins, which act as light sensors in the eye, bacteriorhodopsin actually transforms light energy. This energy conversion is connected with the asymmetric incorporation of bacteriorhodopsin in the lattice structure of the purple membrane which forms patches on the cell surface of halobacteria. Alongside the chlorophyll system, the purple membrane system represents the second light energy conversion principle to be discovered in living nature. Bacteriorhodopsin acts as a light-driven proton pump or as the main component of such a pump system. Absorption of light triggers off a cycle of reactions coupled with the spatially oriented uptake and release of a proton. In the intact cell an electrochemical gradient is thus built up across the cell membrane of the bacterium in which part of the absorbed light energy is stored and which is not dependent upon redox processes as in the case of respiration or photosynthesis. This electrochemical gradient can supply the energy required for ATP synthesis in the cell; a reversible proton-translocating ATPase serves as catalyst system.     

A π-acceptor series for phosphines from51V N.M.R. data on [η5-CpV(CO)3L] complexes

Summary Qualitative molecular orbital considerations of the complexes [⁵-CPV(CO)₃ L] (L = substituted phosphane, SbPh₃, AsPh₃, CN^–) suggest that s' V chemical shift parameters () obtained for these compounds should correlate with the -acceptor abilities of L. Based on observed r-values, the ligands are arranged in sequence of their -acceptor ability, which lies in the order P(OR)₃ > CN^– > PR'₃3 SbPh₃ PPhF₂ > P(i-Bu)₃ P(NR ₂ )₃ > PPh₃ > AsPh₃ Nuclear spin-spin coupling constants J (⁵¹V-³¹ P), line widths H and i.r. data in the (CO) region are also presented.P(OR)₃ = P(OEt)₃, 4-Ethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]-octane; R = Me, n-Pr; R = Me, Et.     

Cycloadditionsreaktionen der aminofluorsilane

Aminofluorsilanes are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines. The reaction of aminofluorosilanes with butyllithium in a (2 + 2)cyclo addition reaction leads to the formation of fourmembered silicon-nitrogen ring compounds. The mechanism of the reaction is discussed, the mass, ¹H and ¹⁹F NMR spectra of the compounds are reported.     

The Yellow Polymorphs of Mercuric Iodide (HgI2)

HgI₂ crystallizes under ambient conditions from various solvents and by sublimation into three concomitant polymorphs whose colors are red, orange, and yellow. The orange and yellow phases are metastable and transform into the red phase when touched. A phase transition from red to yellow occurs at 400 K. The reverse transition from yellow to red shows a huge hysteresis. We established that the structures of the metastable yellow^M phase (determined by single‐crystal X‐ray diffraction) and the high‐temperature yellow^HT phase (determined by powder synchrotron X‐ray diffraction and second‐harmonic generation) are different, albeit closely related. Both show analogous packings of I? Hg? I molecules, which are straight in the first and bent with an angle of ca. 160° in the second. The red and orange phases are tetrahedral semiconductor structures that sublime even at room temperature. The growth of the yellow^M phase from 2‐chloroethanol and the kinetics of the reconstructive phase transition red to yellow^HT and back were studied by optical microscopy, Raman spectroscopy in solution, luminescence, and powder synchrotron X‐ray diffraction as a function of time at various temperatures. Both yellow phases grow by accretion of HgI₂ molecules, present in the solution or liberated from the red crystals, on the surface of the crystal. In contrast, the reverse transformation from yellow to red occurs in the bulk of the crystal, presumably by migration of Hg in the packing of I and subsequent rearrangement of I. The displacement parameters of Hg in both structures are considerably larger than those of I and apparently not dominated by disorder effects.     

Synthesis of β3‐Homophenylalanine‐Derived Amino Acids and Peptides by Suzuki Coupling in Solution and on Solid Support

β‐Peptides and, to a certain extent, also mixed α,β‐peptides, are resistant to degradation by a variety of proteolytic enzymes that rapidly degrade natural α‐peptides. This is one of many characteristics that make β‐peptides an attractive class of compounds for drug‐discovery studies. On the other hand, modern organometallic reactions such as the Suzuki–Miyaura cross‐coupling have become standard tools in industry laboratories to derivatize side chains of α‐peptidic compounds to build up libraries of unnatural peptides. Combining both features, we prepared (4‐bromo)‐β³‐homophenylalanine derivatives 3 – 5 and 12 as precursors for Suzuki–Miyaura couplings. From these bromo compounds, we synthesized biaryl‐substituted β‐homoamino acids 6 , and analogs 13 and 15 of the anti‐AIDS drug Saquinavir.     

Investigation of the Interactions of β‐Peptides with DNA Duplexes by Circular Dichroism Spectroscopy

The interaction of β‐peptides with the DNA duplexes of dA₂₀dT₂₀ and a GCN4‐binding CRE sequence was examined. To gauge the factors that govern these interactions, two β‐pentadecapeptides, 1 and 2 , a β‐dodecapeptide, 3 , three β‐decapeptides, 4 – 6 , three β‐heptapeptides, 7 – 9 , and β‐octaarginine 10 were designed and synthesized. The β‐peptides were conceived to adopt a β‐peptide 3₁₄ helix, in which the side chains at position i and i + 3 are aligned vertically along one side of the helix. The side chains of Lys, Asn, and Arg were positioned such that potential H‐bonding sites were created for a helical conformation to interact with the base pairs of DNA. CD Analysis showed that β‐peptides 1, 2 , and 10 interacted with dA₂₀dT₂₀. In addition, β‐peptides 1 and 2 showed significant interaction with a DNA‐duplex 20mer containing the ATF/CREB recognition sequence for the regulatory protein GCN4. It is impossible, at this stage of the investigation, to make a safe proposal about the actual nature of the interaction of the structures(s) of the complexes, the formation of which is suggested by the CD spectra reported herein.     

Syntheses for 2-hydroxy-2H-1,4-benzothiazin-3(4H)-one derivatives as thio analogues of natural hemiacetals

Reductive cyclizations of methyl 2-(2-nitrophenylthio)acetate 2 by means of electrochemistry or by catalytic hydrogenation have been used as key steps in the syntheses of the hemiacetals 2-hydroxy-2H-1,4-benzothiazin-3(4H)-one 10 and its 4-hydroxy derivative 9 representing thio analogues of allelo chemicals found in Gramineae and Acanthaceae. In contrast to its natural counterpart 2,4-dihydroxy-2H-1,4-benzoxa-zin-3(4H)-one hydroxamic acid 9 did not undergo degradation by extrusion of formic acid.     

Some non-existence results on divisible difference sets

In this paper, we shall prove several non-existence results for divisible difference sets, using three approaches:

1. character sum arguments similar to the work of Turyn [25] for ordinary difference sets,
2. involution arguments and
3. multipliers in conjunction with results on ordinary difference sets.

Among other results, we show that an abelian affine difference set of odd orders (s not a perfect square) inG can exist only if the Sylow 2-subgroup ofG is cyclic. We also obtain a non-existence result for non-cyclic (n, n, n, 1) relative difference sets of odd ordern.     

Reconstructing phase space from PDE simulations

We propose the Karhunen-Loève (K-L) decomposition as a tool to analyze complex spatio-temporal structures in PDE simulations in terms of concepts from dynamical systems theory. Taking the Kuramoto-Sivashinsky equation as a model problem we discuss the K-L decomposition for 4 different values of its bifurcation parameter . We distinguish two modes of using the K-L decomposition: As an analytic and synthetic tool respectively. Using the analytic mode we find unstable fixed points and stable and unstable manifolds in a parameter regime with structurally stable homoclinic orbits (=17.75). Choosing the data for a K-L analysis carefully by restricting them to certain burst events, we can analyze a more complicated intermittent regime at =68. We establish that the spatially localized oscillations around a so called strange fixed point which are considered as fore-runners of spatially concentrated zones of turbulence are in fact created by a very specific limit cycle (=83.75) which, for =87, bifurcates into a modulated traveling wave. Using the K-L decomposition synthetically by determining an optimal Galerkin system, we present evidence that the K-L decomposition systematically destroys dissipation and leads to blow up solutions.We would like to dedicate this paper to Klaus Kirchgässner on the occasion of his 60th birthday     

Unified treatment of fermions and bosons

Dirac's matrices can be interpreted as an 8-rank covariant antisymmetric tensor field on an 11-dimensional manifold (space-time ×S ⁷) enforcing a linkage between the Lorentz transformation and rotations ofS ⁷, conferring spinorial properties on any quantity having an index in the inner spaceS ⁷.