Quantitative gas-liquid chromatography of iproniazid and iproclozide.

Analytically packed columns prepared with Versamid-930, Versamid-900, XE-60, and OV-225 as stationary phases were examined for quantitative gas-liquid chromatography of the potent monamine oxydase inhibitor (MAOI) drugs iproniazid and iproclozide. With the aid of chemically related substances as internal standards, response ratios were determined and linearities calculated by regression analysis. Using the 2-butyl analogs of compounds all four column systems permit quantitation of iproniazid and iproclozide with a percent standard deviation sigmaK of about 1% or less.     

Direct immobilization of native yeast iso-1 cytochrome C on bare gold: fast electron relay to redox enzymes and zeptomole protein-film voltammetry

Cyclic voltammetry shows that yeast iso-1-cytochrome c (YCC), chemisorbed on a bare gold electrode via Cys102, exhibits fast, reversible interfacial electron transfer (k(0) = 1.8 x 10(3) s(-1)) and retains its native functionality. Vectorially immobilized YCC relays electrons to yeast cytochrome c peroxidase, and to both cytochrome cd(1) nitrite reductase (NIR) and nitric oxide reductase from Paracoccus denitrificans, thereby revealing the mechanistic properties of these enzymes. On a microelectrode, we measured nitrite turnover by approximately 80 zmol (49 000 molecules) of NIR, coadsorbed on 0.65 amol (390 000 molecules) of YCC.     

Nuclear magnetic resonance studies of sulfur inversion in bis(cyclopentadienyl)-molybdenum and -tungsten complexes with dithioethers

The metallocene thioether derivatives [Cp₂M(MeSCH₂CH₂SMe)][PF₆]₂ (1, M = MO; 2, M = W), [Cp₂Mo(SCH₂CH₂SMe)][PF₆] (3) and [Cp₂M(SCH₂CH₂S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol⁻¹), 2 (51.2 ± 4.6 kJ mol⁻¹) and 3 (30.0 ± 3.1 kJ mol⁻¹). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour.     

Determination of rate constants and reaction orders with an open-closed flow-injection configuration

A new, very useful application of open-closed configurations to kinetic studies is reported. The multipeak recordings provided by the manifold used, which features a single conventional photometric detector, were used to calculate the rate constants and reaction orders of a chemical system, namely the ligand displacement reaction between the cobalt(II)-EGTA complex and PAR.     

Partially and totally asynchronous algorithms for linear complementarity problems

A unified treatment is given for partially and totally asynchronous parallel successive overrelaxation (SOR) algorithms for the linear complementarity problem. Convergence conditions are established and compared to previous results. Convergence of the partially asynchronous method for the symmetric linear complementarity problem can be guaranteed if the relaxation factor is sufficiently small. Unlike previous results, this relaxation factor interval does not depend explicitly on problem size.This material is based on research supported by the Air Force Office of Scientific Research Grant No. AFOSR-89-0410.The author wishes to thank the referee for pointing out how to improve the bound (12). The same technique can be used to reduce the factorn in Ref. 5, p. 553, to .     

MPT versus: A manifestly covariant presentation of motion reversal and particle-antiparticle exchange

We show that particle-antiparticle exchange and covariant motion reversal are two physically different aspects of the same mathematical transformation, either in the prequantal relativistic equation of motion of a charged point particle, in the general scheme of second quantization, or in the spinning wave equations of Dirac and of Petiau-Duffin-Kemmer. While, classically, charge reversal and rest mass reversal are equivalent operations, in the wave mechanical case mass reversal must be supplemented by exchange of the two adjoint equations, implying .Denoting by M the rest mass reversal, P the parity reversal, T the Racah time reversal, and Z the exchange, the connection with the usual scheme of charge conjugation, parity reversal, and Wigner motion reversal, is with, of course,     

Zur Synthese von Human-Big-Gastrin I

The synthesis of the tetratriacontapeptide amide corresponding to the revised primary structure of human big gastrin I is described. For this purpose the fragments were designed in view of the maximum use of those utilized in our previous synthesis of human big gastrin I according to the first sequence proposal. Consequently the key tripeptide-Pro-Pro-His- (sequence 7–9) was prepared in suitably protected form to be used as amino or carboxyl component for assembly of the segments 1–9 and 1–14, respectively. Final condensation of the latter nona- and tetradecapeptide derivatives with the C-terminal segments 10–34 and 15–34 via the azide and the dicyclohexylcarbodiimide/N-hydroxysuccinimide procedure, respectively, leads to crude fully protected human big gastrin I. Upon deprotection by exposure to trifluoroacetic acid in presence of ethanedithiol-(1,2) as scavanger, ion exchange chromatography and partition chromatography, the desired tetratriacontapeptide amide was isolated in satisfactory yield with a high degree of purity. The identical immunological behaviour of the synthetic material, if compared with that of natural human big gastrin I, represents ulterior strong evidence for the correctness of the newly proposed structure for this putative prohormonal form of the gastrins.

Kurzmitteilung:Wünsch E., Wendlberger G., Mladenova-Orlinova L., Göhring W., Jaeger E., Scharf R., Gregory R. A., Dockray G. J., Hoppe-Seyler's Z. Physiol. Chem.362, 179 (1981).