Towards Diastereomeric Pure Salts with Antisolvent Methods

Chiral molecules, especially enantiomers and diastereomers of purity > 99 %, present a significant market share within the chemical, pharmaceutical, and flavor industries. Antisolvent precipitations, both batch and semicontinuous operations to serve the current trends in flow chemistry were demonstrated to be environmentally benign and efficient tools in achieving high optical purities. Although salts are known to be insoluble in supercritical CO₂, instabilities of the nascent salts were detected and applied for increasing efficiency. Diastereomeric excess values of the crystalline products exceeded 99 % in maximum of three consecutive steps both by repeated resolution with half molar equivalent of the amine to the acid and by direct recrystallization of the salts.     

Van vleck paramagnetism of the diluted intermetallic compounds Pr1−x Y x Ni5 at fields up to 15 T

We have measured the 16 Hz susceptibility of the diluted Van Vleck paramagnets Pr_1−x Y _x Ni₅ withx=0.00, 0.05, 0.10. 0.20 at temperatures 1.5 K≤T≤50 K and magnetic fields up to 15T. Their Van Vleck type magnetic susceptibility χ(T, B, x) strongly depends on the field atB≥6 T. The temperatureT _max(B, x) of the maximum of χ(T, B, x) decreases at increasing the field from zero to 15 T by approximately one order of magnitude for all Pr_1−x Y _x Ni₅ compounds. Changing the dilutionx from zero to 0.20, the field whereT _max(B, x) strongly drops is increased from 9 T to 11 T. Our data agree qualitatively with the predictions of a point charge model which considers the Zeeman term in addition to the electronic exchange and the dominating crystal field contributions.     

Persistent GAD 65 antibodies in longstanding IDDM are not associated with residual beta-cell function, neuropathy or HLA-DR status

Persistent humoral autoimmunity to the enzyme glutamic acid decarboxylase (GAD) has been described in a substantial proportion of patients with insulin-dependent diabetes mellitus (IDDM) of long duration. The source of the stimulus for this autoimmune reactivity is still unknown. Because the GAD 65 isoform is mainly expressed in pancreatic beta-cells and in the nervous system we investigated in the present study of the largest number of well characterized patients with longstanding IDDM (n = 105; median duration: 21 years; range: 10-46 years) the presence of autoantibodies to GAD 65 and their relationship to a residual C-peptide response or peripheral and autonomic neuropathy. Additionally we studied the HLA-DR status relative to GAD 65 antibodies in 86 out of the 105 individuals. One hundred healthy control subjects and 100 recent onset IDDM patients were also studied for GAD 65 antibodies. GAD 65 antibodies were detected in a radioligand-binding-assay with recombinant human GAD 65 and were present in 32% of the long-term diabetic patients, 82% of the recent onset IDDM patients and in 3% of the healthy control subjects. A preserved C-peptide response to i.v. glucagon (Hendriksen criteria) was observed in 23% of the long-term IDDM patients. Autonomic neuropathy and peripheral neuropathy was identified using criteria based on both symptoms and formal testing giving a frequency of 67% vs 79%. The HLA specific DR 4/X was observed in 47% and HLA-DR 3/X in 22% of the long-term IDDM patients. Patients who were heterozygous for DR3/DR4 were found in 23% of the cases. GAD 65 antibodies were significantly less frequent in the long-term IDDM patients compared to recent onset IDDM (p < 0.001), and diabetes duration showed a significant negative correlation with GAD 65 antibody index levels (r = 0.22, p < 0.01). Interestingly, GAD 65 antibodies were not significantly correlated either with residual beta-cell function or neuropathy and no particular HLA-DR status was associated with persistent GAD 65 antibodies. In conclusion neither residual beta-cell function nor diabetic neuropathy or a certain HLA-DR specificity are exclusively associated with persistent autoimmunity directed to GAD 65 in longstanding IDDM. The stimulus for the persistent humoral immune response and its significance for the disease process and its complications remain to be established.     

The influence of various reaction parameters on the performance of (α‐diimine)nickel(II) catalysts in ethylene oligomerization reactions

Modified (α‐diimine)nickel(II) catalysts are suitable for ethylene oligomerization reactions. Due to the mechanism (“chain running”), the formation of double‐bond isomers and branched olefins can be observed. The obtained oligomer mixtures show a Schulz–Flory distribution. Increasing ethylene pressure favors the selectivity of α‐olefin formation. The same effect can be observed when Lewis bases like thiophene or furane are added to the oligomerization reaction mixture. These results can be related to an interaction of the additives with the catalytic active species during the oligomerization process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1356–1361, 2003     

The High Field Project at Dresden/Rossendorf: A Pulsed 100 T/10 ms Laboratory at an Infrared Free-Electron-Laser Facility

This article describes the project to build a pulsed magnetic field user laboratory at the Forschungszentrum Rossendorf near Dresden. Using a 50 MJ/24 kV capacitor bank, pulsed fields and rise times of 100 T/10 ms, 70 T/100 ms, and 60 T/1 s should be achieved. The laboratory will be built next to a free-electron-laser-facility for the middle and far infrared (5 to 150 µm, 2 ps, cw). We describe the work which has been performed until now to start the construction of the laboratory in 2003: coil concepts and computer simulations, materials development for the high field coils, and design of the capacitor bank modules. In addition, a pilot laboratory has been set up where fields up to 62 T/15 ms have been obtained with a 1 MJ/10 kV capacitor module. It is used to gain experience in the operation of such a facility and to test various parts of it. In this test laboratory special devices have been developed for measurements of magnetization and magnetoresistance, and have been successfully used to investigate various materials including semiconductors and Heavy Fermion compounds. In particular, metamagnetic transitions in intermetallic compounds and the irreversibility field of a high-T _c superconductor have been determined. Shubnikov–de Haas oscillations have been observed in the semimetallic compound CeBiPt. Resistance relaxation has been observed to start less than 1second after the field pulse. It could be shown for the first time that nuclear magnetic resonance (NMR) is detectable in pulsed fields.     

Stoichiometric dye-binding procedure for the determination of the reactive lysine content of soya bean protein

A new analytical method has been developed for the determination of the reactive lysine content of soya bean protein. The method is based on the reaction of the free basic groups of the protein with 1-phenylazo-2 naphthol-6,8 disulphonic acid. With regard to the stoichiometry of the procedure, it has been proved, contrary to earlier reports, that the basic amino acids, histidine, arginine and lysine, each combine with one mole of the dye. After acylation with propionic anhydride lysine alone loses its dye reactivity. The usefulness of the proposed method has been demonstrated by the determination of the reactive lysine content of several untreated, heat-treated and acid-treated soya bean samples. The results show that heat damage of about 5% in reactive lysine content can be measured in 1·5 h with good reproducibility.     

Modeling study of migration-driven lateral instability in autocatalytic systems

The lateral stability of reaction fronts in simple autocatalytic models with the components carrying various charges is investigated when the system is exposed to an inhomogeneous electric field parallel to the direction of propagation. The enhanced migrational flux of the reactant destabilizes the planar front giving rise to a cellular structure because the electric field strength is greater on the reactant side of the reaction front. The onset of instability depends not only on the charge difference between the reactant and the autocatalyst but also on the variation of specific conductance in the course of the reaction, which results in a difference in electric field strength on the opposite sides of the reaction front.     

Water uptake of water-borne paint resin films as studied by impedance spectroscopy and gravimetry

Impedance spectroscopy and gravimetry were employed to characterize alkyd-acrylate and styrene-acrylate water-borne resin film properties during wetting-through (i.e. during water uptake).