Preparation and redox properties of N,N,N-1,3,5-trialkylated flavin derivatives and their activity as redox catalysts

Eight different flavin derivatives have been synthesized and the electronic effects of substituents in various positions on the flavin redox chemistry were investigated. The redox potentials of the flavins, determined by cyclic voltammetry, correlated with their efficiency as catalysts in the H2O2 oxidation of methyl p-tolyl sulfide. Introduction of electron-withdrawing groups increased the stability of the reduced catalyst precursor.     

The second virial coefficient of 3-centerLennard-Jones molecules and its relation to 1- and 2- center molecules

The second virial coefficients of homonuclear three-centerLennard-Jones molecules are calculated with various parameters of the isosceles triangle connecting the three sites. A special effort is made to establish the reducedBoyle temperaturesT _B and the values of the second virial coefficients atT/T _B=0.3 for the sake of comparison with one- and two-centerLennard-Jones molecules. It is shown that it is possible to find parameter values of the interaction potential of one- and two-centerLennard-Jones molecules which give very similar values of second virial coefficients forT/T _B0.3, and the equivalence conditions are established. These conditions might not only give a basis for a microscopic scaling of state variables, but also some restrictions for the validity of the group contribution concept.Presented in part at the DFG-Colloquium at Paderborn, 19th April 1982, and at the 5th Conference on Mixtures of Nonelectrolytes and Intermolecular Interactions, April 18–22, 1983, at Halle (GDR).     

Deoxygenation of supporting electrolytes in stripping voltammetry by glocuse and co-immobilized glocuse oxidase and catalase in a flow system

Carrier solutions for stripping voltammetry in flow systems are deoxygenated by reaction with glucose added to the carrier. The reaction was catalyzed by glocuse oxidase and catalase co-immobilized in an enzyme reactor which was inserted before the injector. The oxygenated was removed at least as efficiently as with nitrogen purging and the voltametric behaviour of cadmium(II), lead(II) and zinc(II) was unaffected by the glucose/gluconic acid system. A particular advantage is the rapid start-up compared to the lengthy purging of carrier solution when nitrogen degassing is used. The enzyme reactor made from porous glass was effective for several months.     

A simple adsorption model for ionic surfactants

In the past, few theoretical attempts have been made to describe quantitatively the adsorption of ionic surfactants at liquid interfaces. Well-known adsorption isotherms due to Frumkin or Hill–de Boer cannot respond to the specific electrostatic and geometric properties of the surfactant molecules. Our approach is based on a combination of the Gouy–Chapman theory with a modified Frumkin isotherm. The modification implies that the system is free to choose an optimal head group area and an optimal arrangement of the surfactant molecules in the interface as a function of bulk concentration. Interaction energies between neighbouring adsorbed surfactant molecules and between surfactant and water molecules are taken into consideration. The minimum of the Gibbs free energy of the system is equivalent to a minimal interfacial tension. Thus, the thermodynamically stable isotherm can be obtained as the lower envelope of the family of σ versus ln c isotherms resulting from different choices of the model parameters, including the area per molecule. According to the Gibbs equation, the Γ versus ln c adsorption isotherm is obtained as the derivative of this envelope. By variation of the model parameters, the envelope of the calculated adsorption isotherms can be fitted to experimental data of the interfacial tension versus bulk concentration. A computer program is used to calculate the σ versus c and the Γ versus ln c curves as well as to fit the parameters. Received: 28 October 1999/Accepted: 8 February 2000     

Copper and Silver Atoms in the β-Cage of a Zeolite: Model Calculations

The electronic structures of the 4-4 SBU, the β-cage, and the β-cage with two 4-4 SBU's attached to it have been studied by means of EH-MO calculations. No indication of the formation of a band structure has been found. The HOMO region consists of many closely spaced, localized states, 98.6% of them concentrated on the O-atoms. Reversible color changes of Cu⁺¹ and Ag⁺¹ zeolites observed upon hydration-dehydration experiments can be understood as charge-transfer transitions from the HOMO concentrated on the zeolite O-atoms to the metal cations. As soon as the Cu⁺¹ or Ag⁺¹ are partially hydrated, the ns* and np* states are shifted to higher energies. The luminescence observed with dehydrated Cu⁺¹-zeolites X is caused by a 4p*←HOMO absorption, followed by spontaneous 4s*←4p* emission. After a detailed study of a Cu⁺¹ in the 6-6 SBU, we discuss the electronic structure of a β-cage filled with 1,2,4,8, and 9 Cu⁺¹. In each case, the β-cage is found to be too small to allow the formation of a band structure. The levels caused by the added copper are distinctly quantized. Calculations on [Ag₃(H₂O)₃]³⁺ in a β-cage are reported. The direct interaction between the Ag-atoms is significant. As a consequence, the states formed by Ag 5s and 5p atomic orbitals are delocalized over the three Ag-centers. In both the Cu⁺¹ and the Ag⁺¹ zeolites, the ligand-field picture is found to be insufficient to explain the electronic structure, when the metal is coordinated to the zeolite oxygen framework.     

Deviation from Ohm's law in electric field assisted capillary liquid chromatography

Earlier studies of electric field assisted LC (EF-LC) have shown that the effect on charged analytes of the application of an electric field over a capillary LC column is relatively small. Charged analytes can only be affected by the electric field while present in the mobile phase, which makes the effective time for influence of the electric field t(0) independent of retention time. Because the charged analytes only can be affected for a short time the electric field strength ought to be high in order to increase the impact of the electric field on the separation. We have, however, found that only a relatively low electric field strength can be used in EF-LC when pressure is used as main driving force. The useful field strength was limited by a dramatic increase in the current. This increase in current was found to origin from an increased concentration of buffer ions that have an electrophoretic mobility towards the pumped flow.     

Retention behavior and solvent optimization of organochlorine pesticides in solid-phase extraction

Summary Plots of capacity factor and retention time vs. elution solvent composition were proved to be useful to interpret the retention behavior of Kepone and its metabolites in a reversed-phase solid-phase extraction and to optimize the elution solvent. The percent recovery of Kepone was largely improved when the solvent was optimized. The standard deviations of the results of extractions were also improved upon the optimization of the solvent.     

Estimation of third virial coefficients at low reduced temperatures

We use the Clausius–Clapeyron equation to calculate third virial coefficients at low reduced temperatures. This procedure gives an alternative to predict third virial coefficients in a region where the third virial coefficient is difficult to measure. We compare the results of this method with published third virial coefficient data. Calculated third virial coefficients have average percentage deviations within 5% of the experimental values at reduced temperatures between 0.8 and 1.0.     

Derivatives and reactions of glutaconaldehyde—XIII: Regiospecific ring opening of 3-substituted pyridines

A number of nucleophilic ring openings of 3-substituted pyridinium salts have been reinvestigated and summarized. The structure of the resulting stable glutaconaldehyde derivatives was investigated in detail by ¹H NMR. It has been concluded that in general nucleophilic pyridinium ring openings are highly regiospecific. In each case investigated to date a single product was isolated, as a result of attack by the nucleophile at only one of the pyridine α-positions. With the OH ion as the only nucleophile, attack occurs at the pyridine C-2, while larger nucleophiles such as amines and carbanions attack at the pyridine C-6. This was found to be the case for a variety of 3-substituted pyridines such as 3-methyl, 3-methoxy-, 3-cyano-, 3 chloro-pyridine.     

FLUORESCENCE PROPERTIES OF PORPHYRIN-GLOBIN FROM HUMAN HEMOGLOBIN

Fluorescence excitation and emission spectra, decays, and quantum yields are reported for the porphyrin-globin of hemoglobin (Hb^desFe) in aqueous solution of pH 8, at 4°C. A very weak fluorescence was observed in the UV (maximum at 334 nm), due to tryptophan and tyrosine residues, in addition to the strong porphyrin emission in the visible (maxima at 624 and 692 nm) reported previously. The absorption and fluorescence properties of the porphyrins of Hb^desFe were compared to those for free porphyrin in organic solvents and in aqueous solution. The close similarity of the fluorescence decays and quantum yields in Hb^desFe and in solution indicate the absence of stronger, specific porphyrin-protein interactions; however, slight spectral shifts point to the existence of water molecules in the Hb^desFe porphyrin environment. The fluorescence study also demonstrates the existence of efficient Trp-porphyrin energy transfer of Förster type. The extent of transfer is in satisfactory agreement with the value expected from crystallographic data for hemoglobin. The results are discussed and compared to previous fluorescence studies of hemoglobin and apohemoglobin. An improved method for the preparation of Hb^desFe is reported.