CHEMICALLY MODIFIED PHOTOSYNTHETIC BACTERIAL REACTION CENTERS: CIRCULAR DICHROISM, RAMAN RESONANCE, LOW TEMPERATURE ABSORPTION, FLUORESCENCE AND ODMR SPECTRA AND POLYPEPTIDE COMPOSITION OF BOROHYDRIDE TREATED REACTION CENTERS FROM Rhodobacter sphaeroides R26

Abstract— Reaction centers from Rhodobacter sphaeroides have been modified by treatment with sodium borohydride similar to the original procedure [Ditson et al., Biochim. Biophys. Acta 766 , 623 (1984)], and investigated spectroscopically and by gel electrophoresis.
(1) Low temperature (1.2 K) absorption, fluorescence, absorption- and fluorescence-detected ODMR, and microwave-induced singlet-triplet absorption difference spectra (MIA) suggest that the treatment produces a spectroscopically homogeneous preparation with one of the 'additional' bacteriochlorophylls being removed. The modification does not alter the zero field splitting parameters of the primary donor triplet (^TP870).
(2) From the circular dichroism and Raman resonance spectra in the1500–1800 cm^-1 region, the removed pigment is assigned to Bchl_M, e.g. the "extra" Bchl on the "inactive" M-branch.
(3) A strong coupling among all pigment molecules is deduced from the circular dichroism spectra, because pronounced band-shifts and/or intensity changes occur in the spectral components assigned to all pigments. This is supported by distinct differences among the MIA spectra of untreated and modified reaction centers, as well as by Raman resonance.
(4) The modification is accompanied by partial proteolytic cleavage of the M-subunit. The preparation is thus spectroscopically homogeneous, but biochemically heterogenous.     

Rotational-diffusion anomalies in dye solutions from transient-dichroism experiments

Subnanosecond transient-dichroism experiments have been performed to investigate the rotational diffusion of dyes in solution. Dyes and solvents were chosen in a way to obtain information on the influence of size, shape and hydrogen-bonding abilities either of the solute or the solvent molecules. One finds slow orientational relaxation of di-anionic xanthene dyes in alcohols, while oblate cationic dyes rotate faster in spite of their comparable size. The rotational diffusion times for alcohol solutions exceed the theoretical values predicted by the Debye-Einstein model except for prolate molecules. For a solute molecule with internal mobility the rotational diffusion exhibits a partial slip behaviour. It is shown that the deviations from the Debye-Einstein model are restricted to alcohols since for other solvents either with or without strong hydrogen-bonding abilities the experimental values agree with the hydrodynamic model including the stick-boundary condition. Experiments on erythrosine B reveal the influence of size and shape of the attached solvent molecules.     

Schwingungsspektren und Kraftkonstanten von Hexamethyldisilan,Hexaphenyldisilan und 1,1,1-Trimethyl-2,2,2-triphenyldisilan

The Raman and infrared spectra of (CH₃)₃SiSi(CH₃)₃ (I), (CD₃)₃SiSi(CD₃)₃, (C₆H₅)₃SiSi(C₆H₅)₃ (II), (CH₃)₃SiSi(C₆H₅)₃ (III), and (CD₃)₃SiSi(C₆H₅)₃ are reported. Assignments are based on symmetry G ₃₆ ⁺ (free internal rotation) forI, D_3d forII, and C_3v forIII. Normal coordinate treatment has been done using some simplifications in the phenyl coordinates. The SiSi stretching force constant inI amounts to 1,65 N/cm. In compoundsII andIII strong vibrational coupling is elucidated byPED calculations.     

Bindungsverhältnisse und Elektronenverteilung im Br 4 2− -Ion

The linear ions Br ₄ ^2– which has been discovered for the first time by Siepmann and Schnering [13] in W₆Br₁₆ have been studied theoretically using the free electron model for the valence electrons. Electronic structure, binding energy and charge distribution show that Br ₄ ^2– is a typical electron deficient compound stabilized by a 4c-6e bond.

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Herrn Prof. Dr. H. Dunken bin ich für sein stetes Interesse und die rege Anteilnahme an diesen Modellrechnungen zu großem Dank verpflichtet.     

The role of triplet states in dye sensitization of ZnO electrodes

The quantum efficiency of photooxidation of a number of xanthene dyes at ZnO single crystal electrodes has been found to depend on the solution concentration of a triplet quenching agent, FeCN^4?₆, providing evidence for triplet state participation in the oxidation reaction.     

Über Pterinchemie. 49. Mitteilung. Eine neue Synthese von 5-Formyl-6, 7-dimethyl-5,6,7,8-tetrahydropterin und 5,6,7-Trimethyl-5,6,7,8-tetrahydropterin

Starting with 5-formyl-6,7-dimethyl-5,6,7,8-tetrahydropterine (II), a new synthesis of 5,6,7-trimethyl-5,6,7,8-tetrahydropterine (III) is described. Thereby the chemical behaviour of the 5-formyl group in II is investigated, in order to enable the unequivocal differentiation between formylation at position 5 and at position 10 in folic and tetrahydrofolic acid derivatives. ¹³C-NMR. spectra of II and III are discussed.     

Determination of lithium in human serum by electrothermal atomic absorption spectrometry

An efficient method was developed for the determination of nanogram levels of lithium in biological samples. Serum samples from human subjects from southeastern Spain, treated or not treated with lithium carbonate, were analyzed by electrothermal atomic absorption spectrometry. The samples were previously treated with a matrix modifier consisting of 0.1% Triton X-100 and injected through a graphite tube with L'vov platform. The Li concentrations measured by the procedure described for the 3 certified reference samples used were not significantly different (p > 0.05) than certified levels. Sample recoveries and variability during several days, with coefficients of variation from 4.00 to 14.8%, demonstrated the reliability and accuracy of this technique. Mean Li concentration determined in the serum of individuals with psychiatric disorders treated with Li (n = 117, 5.077 +/- 1.795 microg Li/mL) was significantly higher (p < 0.001) than that in individuals not treated with Li (n = 24, 1.902 +/- 2.054 ng Li/mL).     

Rapid flow-injection sandwich-type immunoassays of proteins using an immobilized antibody reactor and adenosine deaminase-antibody conjugates

A rapid flow-injection sandwich enzyme immunoassay suitable for the direct determination of proteins in biological samples is described. The proposed system utilizes highly active adenosine deaminase—antibody conjugates in conjunction with a flow-through immunoreactor and an ammonium ion-selective potentiometric detector. After appropriate sample/reagent injection steps, the enzyme activity bound to the reactor is measured by diverting a coninuously flowing stream of substrate (adenosine) through the packed immunocolumn and detecting liberated ammonium ions downstream with a tubular ammonium ion-selective electrode. The bound enzyme activity is directly proportional to the concentration of analyte in the original sample. By using non-equilibrium flow-rates of sample and reagent slugs, a single protein assay takes less than 12 min, including regeneration of the reactor. The proposed method is shown to be selective, reproducible and capable of determining accurately the model protein (human IgC) at sub-μg ml^?1 concentrations.     

Use of diode-array detectors for the simultaneous spectrophotometric determination of calcium and magnesium by flow injection

A method for the simultaneous flow injection spectrophotometric determination of calcium and magnesium with Arsenazo III based on the use of diode-array detector and merging zones is described. The method is applicable to the resolution of mixtures in which the chromogenic reagent has a high absorbance and its spectrum strongly overlaps those of its complexes. In resolving the mixtures, the excess reagent is considered as another component. Quantitation is based on the normal absorbance and first-derivative absorbance spectra. The method is applied to 0.2–1.5 μg ml^?1 Ca and 0.1–1.0 μg ml^?1 Mg. The analysis rate is 50 h^?1.