Cover Picture

The cover picture shows a model of the "progenitor-TADDOLs" in front of a panorama of the Fünffingersstocks and the Wenden Glacier in the Titlisgebiet (Switzerland). The model is flanked by a stylized view of the general mechanistic model for the preferred stereochemical pathway of the Ti-TADDOLate-catalyzed reaction of chelating substrates (left) and a blackboard (right) showing formulae of compounds that can be prepared with high enantioselectivity by nucleophilic addition in the presence of titanium TADDOLates. From TADDOL, introduced in 1982, a genuine auxiliary system for the "introduction of chirality" (not only by reaction) has been developed, which, in the final sprint against the competition has a good chance of securing a place on the winning podium. The photograph of the mountain landscape was taken by Dr. J. Frackenpohl, the cover picture was generated by one of the authors (A.H.) of the comprehensive review of TADDOLs in this issue (p. 92 ff.) with the help of the program Povray. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author.     

Analysis of ion binding on humic substances and the determination of intrinsic affinity distributions

Humic substances are characterized by a variable electric potential and by a variety of binding sites leading to chemical heterogeneity. Binding of ions to these substances is influenced by both factors. A methodology based on acid—base titrations at several salt levels is presented that allows for the assessment of an appropriate electrostatic double-layer model and the intrinsic proton affinity distribution. The double-layer model is used for the conversion of pH to pH_S for each data point, where H_S is the proton concentration in the diffuse layer near the binding site. It is shown that with an appropriate double-layer model the proton binding curves at different salt levels converge into one “master curve” when plotted as a function of pH_S. The intrinsic proton affinity distribution can then be derived from the “master curve” using the LOGA method. A rigorous analysis of metal binding to humic substances is complex and in practice is not feasible. Under two different (simplifying) assumptions, namely fully coupled and uncoupled binding, it is shown how intrinsic metal ion affinity distributions can be obtained. Model calculations show that apparent metal ion affinity distributions do not resemble the intrinsic metal ion affinity distribution.     

Some aspects of the interactions of orthopositronium with perfect and defect surfaces of insulating materials

ETLA (Elastic Thermalisation Lifetime Analysis) is a new model function for the fitting of lifetime spectra of slowly thermalising orthopositronium in the free space between the grains of insulating oxide powders. From this model one can obtain three fundamental parameters; the mass of the cluster of atoms which scatters the o-Ps, the probability that the o-Ps is forced into two-quantum decay at each collision and the emission energyE(0) of the o-Ps from the powder surface. As a consequence of full thermalisation of the Ps it is shown that the o-Ps quenching constant _q () follows atT ^1/2 dependency for MgO, Al₂O₃ and SiO₂ and for temperatures between 77 and 500 K. In MgO powder at low temperatures the irradiation by the positrons induces surface paramagnetic defects which are identified as Mg⁺ sites. These surface defects do not affect the thermalisation, but they induce paramagnetic o-p conversion i.e., an increase in , and they are also responsible for an increase in the emission energyE(0) of the o-Ps.     

Der “thermo-stat” — eine ergänzung der verfahren zur bestimmung katalytisch wirksamer substanzen

The “Thermo-Stat” — a new device for the determination of catalyticaily active substancesA device for the determination of catalytically active substances, called a “ThermoStat”, is described. An additional heater is used to keep constant an arbitrarily preset temperature gradient between the reaction mixture and a cooling coil. Any heat produced by the catalysed reaction induces a deviation from the preset parameter and thus cuts out the additional heater. These breaks are plotted versus time by an integrating recorder. The slope of the reaction curve obtained is a measure of the concentration of the catalyst. As examples, determinations of copper in the range 0.1–2.0μg and molybdenum in the range 5–50 μg are discussed.     

Beiträge zur Chemie der Pyrrolpigmente, 70. Mitt.: Zum aktiven Transport mit tripyrrinoiden Liganden

The tripyrrin carboxylic acid6 exhibits a pronounced efficiency for carrier mediated proton driven secondary active transport (counter transport) for a series of toxic or valuable cations in a bulk chloroform membrane. In case of Zn⁺⁺ ions the mechanism including complete concentration profiles forNerst diffusion layers and bulk phase have been established. This compound might be used for detoxification or enrichment of precious metals using membrane separation systems.

Herrn Prof. Dr.A. Neckel mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Study of a glassy carbon electrode in amperometric detection using d.c., normal and differential pulse techniques

The results of a comparative study on d.c., normal pulse and differential pulse techniques applied to anodic amperometric detection at a glassy carbon electrode in a voltammetric flow-through cell are presented. The important aspects examined are response time, linearity, limit of detection and selectivity. It is shown that the d.c. mode is the most favourable as long as no adsorption of oxidation products takes place. If strong adsorption occurs, normal pulse detection is recommended, although the limit of detection is somewhat larger.