PHOTOSENSORY BEHAVIOR OF A BACTERIORHODOPSIN-DEFICIENT MUTANT, ET-15, OF Halobacterium halobium

– Halobacterium halobium , strain ET-15, which does not contain detectable amounts of bacteriorhodopsin (BR) shows behavioral responses to UV and yellow-green light. Attractant stimuli. i.e. light-increases in the yellow-green range or light-decreases in the UV, suppress the spontaneous reversals of the swimming direction for a certain time. Repellent stimuli, i.e. light-decreases in the yellow-green range or light-increases in the UV, elicit an additional reversal response after a few seconds. Action spectra of both sensory photosystems, PS 370 and PS 565, were measured with attractant as well as with repellent stimuli. As in BR-containing cells, maximal sensitivity was always found at 370 nm for the UV-system and at 565 nm for the long-wavelength system. Fluence-response curves at 370 and 565 nm obtained with strain ET-15 and with a BR-containing strain show that the sensitivity of both photosystems is not reduced in the absence of BR. It is concluded that BR is required neither for PS 565 nor for PS 370. Instead retinal-containing pigments different from BR have to be assumed to mediate photosensory behavior.     

Structural investigation of high-valent manganese-salen complexes by UV/Vis,Raman, XANES,and EXAFS spectroscopy

XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected.     

Catalyzed Asymmetric Arylation Reactions

Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed.     

SUBSTITUTION OF RETINAL BY ANALOGUES IN RETINAL PIGMENTS OF HALOBACTERIUM HALOBIUM. CONTRIBUTION OF BACTERIORHODOPSIN AND HALORHODOPSIN TO PHOTOSENSORY ACTIVITY

Abstract— In Halobacrerium hnlobium. retinal is the chromophore of the light-energy converting pigments bacteriorhodopsin (BR) and halorhodopsin (HR) and of the sensory photosystems. PS 370 and PS 565. In both photosystems as well as in BR and HR. retinal was substituted by retinal analogues. Retinal₂ ( 3,4-dehydro-retinal ) . shifts the main sensitivity maximum of PS 370 and of PS 565 by about 1.5 nm to longer wavelengths. The absorption maxima of BR and HR are both shifted in the same direction, but by 37 nm. 13-Ethylretinal and 13-propylretirnal shift the main sensitivity maximum of each sensory photosystem to shorter wavclengths; the absorption maxima of BR and HR are shifted in the same direction but to a smaller extent. Both sensory photosystems are equally active with retinal and with each of the three analogues as the chromophore. After substitution of retinal by the analogues, the action spectra of PS 565 of the BR-containing strain R₁L₃ show a secondary bensitivity peak in addition to the main peak. This secondary peak matches the absorption maximum of the corresponding BR. In the action spectra of the BR-deficient strainET–15 this secondary peak is missing. Action spectra of PS 565 of the BR-deficient strainL–33, which synthesizes increased amounts of HR. with all retinals show a secondary peak which matches the absorption maximum of the corresponding HR.
The results show that the analogues can substitute retinal in both sensory pigments as well as in BR and HR. Moreover, the data support the previous assumption that both BRand HR, although not required for photosensory activity can contribute to photosensing through PS 565.     

β relaxation theory for simple systems: some addenda

The evolution of the tagged particle probability density for a hard sphere system is evaluated within the -relaxation window. Relaxation curves obtained by molecular dynamics studies by Barrat, Hansen and Roux for a binary mixture are analyzed quantitatively with -relaxation scaling formulae. The dynamical light scattering data obtained by Pusey and van Megen for colloidal suspensions are described by the combined - and -relaxation scaling results. The range of validity of asymptotic expressions near a glass transition singularity is discussed for the Debye-Waller factor as a function of packing fraction. The applied theoretical formulae are those of the mode coupling theory for the liquid to glass transition.     

Attrition patterns in a high ability programme for precollege students

Completion and performance data from 92 high ability seventh and eighth grade students in an eight‐week summer programme conducted in 1989 and sponsored by the GTE Service Corporation are examined.     

Mesoscopic phase statistics of diffuse ultrasound in dynamic matter

Temporal fluctuations in the phase of waves transmitted through a dynamic, strongly scattering, mesoscopic sample are investigated using ultrasonic waves, and compared with theoretical predictions based on circular Gaussian statistics. The fundamental role of phase in diffusing acoustic wave spectroscopy is revealed, and phase statistics are also shown to provide a sensitive and accurate way to probe scatterer motions at both short and long time scales.