Histidine in enzyme active centers.

The presence of histidine in the active center of an enzyme can be demonstrated by kinetic measurements, chemical modification, NMR spectroscopy or X-ray structure analysis. Histidine is the only naturally occurring amino acid to contain an imidazole residue as a side chain. The role of histidine in enzyme catalysis depends, inter alia, upon the special features of the imidazole residue: it thus tends to form hydrogen bonds, combines donor and acceptor properties and can take part in either nucleophilic or base catalysis. In some of these enzymes the position of each atom is known; however, the theories as to how the catalysis proceeds at a molecular level are controversial.     

Analyse geringer Substanzmengen mit Hilfe der R?ntgenfluorescenzspektrometrie

Zusammenfassung Eine Methode wird beschrieben, die die Analyse sehr geringer Substanzmengen ermöglicht. Eine maximale Einwaage von 2 mg wird in 1 g Borax geschmolzen, und die so erhaltene Boraxscheibe direkt zur röntgenfluorescenzanalytischen Bestimmung der verschiedenen Elemente eingesetzt. Für eine Reihe von Elementen werden die Nachweisgrenzen angegeben und ein Beispiel für die Reproduzierbarkeit der Methode angegeben. Verschiedene Anwendungsbeispiele dieser Methode werden beschrieben und die Ergebnisse mitgeteilt.

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Analysis of very small quantities of substances by X-ray fluorescence spectrometry

A maximum sample weight of 2 mg is molten in 1 g borax und the disk obtained is directly analysed by X-ray fluorescence spectrometry. For a number of elements the limits of detection are given and by one example the reproducibility of the method is shown. Different examples of application are described and the results are presented.

     

Spectroscopy of excited state positronium

Electric dipole transitions in the microwave range have been induced between the fine-structure levels of positronium in the excited staten=2. As an indication of the transitions, we used the increase in Lyman- radiation when the metastable 2³S₁-level is depopulated. The results for the transitions 2³S₁2³P_0,1,2 are ₀=18499.65±1.20±4.00 MHz, ₁=13012.42 ±0.65±1.54 MHz and ₂=8624.38±0.54±1.40 MHz. The first error is statistical and the second systematic. The precision of the present measurement has improved by a factor of 3, compared to previous data. Recent bound state QED-calculations have been extended to the orderR _t8 ⁴ln ^–1. The not yet completely calculated orderR _t8 ⁴ is estimated to contribute less than 1 MHz. Our experimental results are in good agreement with theory. By applying a weak magnetic field, we were able to observe the transition 2³S₁2¹P₁ which is strictly forbidden byC-invariance in zero field. Our result, corrected for Zeeman- and motional Starkeffect, is ₃=11180.0±5.0±4.0 MHz. An upper limit for theC-violating matrix element of MHz could be deduced. Our experiment used moderated slow positrons from the bremsstrahlung and pair production of a pulsed electron linear accelerator (TEPOS facility at the university of Giessen).     

Physicochemical Principles of Extraction with Supercritical Gases

The present review considers some physicochemical properties of fluid mixtures that are of importance for fluid extraction and supercitical fluid chromatography (SFC). Firstly, the important types of phase diagrams are treated, the occurrence of solid phases also being considered in some simple cases. Specific examples are given of mixtures of a highly volatile component I (e.g. CO₂, C₂H₆) with a relatively involatile component II (e.g. squalane) of very different molecular size, shape, structure, and/or polarity, and it is shown how the rather complicated types of phase diagrams can be calculated and correlated. The importance of fluid mixtures extends far beyond the fields of science and technology reviewed.     

PHOTOCHEMICAL RING-OPENING IN meso-CHLORINATED CHLOROPHYLLS

Abstract— Irradiation of 20-chloro-chlorophylls of the a-type with visible light produces long-wavelength shifted photoproducts, which transform in the dark to linear tetrapyrroles (bile pigments). The possible significance for chlorophyll degradation is discussed.     

The Lewis basicity of the [Pt3(μ-CO)3(PR3)3] clusters and the X-ray crystal structure of [{ZnI2}{Pt3(μ-CO)3(PPh(i-Pr)2)3}]

The cluster compounds [Pt₃(μ-CO)₃(PR₃)₃] act as Lewis bases towards the metal halides of Group XI, MX, Group XII, MX₂, and Group XIII, MX₃, to form cluster compounds of the composition [{MX_n}{Pt₃(μ-CO)₃(PR₃)₃}]. The X-ray crystal structure, NMR and IR data are given for the compound [{ZnI}{Pt₃(μ-CO)₃(PPh(i-Pr)₂)₃}].     

1H magic angle rotation NMR in polymer studies

The principles of the method of NMR line narrowing by measurement with spinning of the sample about the magic axis (MAR-NMR) are introduced, with particular emphasis on the effects of internal motion upon the possibilities and limitations of the method. The applications of the method in ¹H-NMR studies of polymer structure and dynamics are then reviewed. Due to both theoretical and experimental limitations, narrowing of dipolar broadened NMR lines by MAR can be observed in ¹H NMR spectra only in those cases where internal motion is anisotropic, or in heterogeneous systems where line width is limited by differences of magnetic susceptibility. In polymers, both solid and liquid, the method makes possible differentiation between isotropic and anisotropic internal motion. In systems with anisotropic internal motion, MAR-NMR makes possible a characterization of motional codes which normally are obscured by residual dipolar interactions, as well as of geometrical restrictions upon these motions.     

Mono-, di-, and trimetallic complexes of the nonalternating polycondensed pi-perimeter decacyclene, C36H18: synthesis, structure, and spectroelectrochemistry of

Reaction of the half-sandwich complexes [(eta5-Me4RC5)M(eta2:O-acac)] (M = Co, Ni; R = Me or Et) with di- and trianions of the polycondensed pi-hydrocarbon decacyclene results in formation of the first Co and Ni triple-decker complexes of this hydrocarbon. For the title compound NMR spectra as well as a crystal structure analysis reveal an antarafacial coordination of two (eta5-Me4EtC5)Co fragments at the central six-membered ring and one of the neighboring five-membered rings of decacyclene. The bridging pi-perimeter decacyclene displays a bowl-shaped topology. In the case of Ni, coordination of two (eta5-Me5C5)Ni fragments at the central six-membered ring of decacyclene is observed, based on the results of 1H and 13C NMR studies. This coordination mode is without precedent for nickel organometallic compounds reported so far. The cobalt complex shows a rich spectroelectrochemistry. Results of cyclic voltammetry and coupled ESR experiments reveal a strong interaction of both metal centers in the mixed-valent monocation of [(eta5-Me4EtC5)Co2(mu-eta5:eta4-C36H18)]. This categorizes the title compound into Robin Day class III.