Vibronic spectral behavior of molecules: XVIII. Theoretical contribution to the S1→S0 fluorescence of the isomeric phenyl naphthalenes within the Herzberg-Teller approach

Theoretical vibronic S₁S₀ line spectra of the isomeric phenyl naphthalenes calculated within the Condon as well as the Herzberg-Teller approaches on the basis of completely optimizedS ₀ andS ₁ molecular geometries, are presented and are contrasted with the experimental fluorescence spectra. The theory-experiment comparison is successful only within the Herzberg-Teller approximation by explicitly including the Dushinsky transformation. An analysis of the significant vibrational modes is given.     

Verfolgung von Phasenreaktionen in Flüssigkeiten

For a great number of processes of technical importance (separation precipitating, adsorption and chemical conversion) an indication of progress of reaction without any temporal delay and gap is required with regard to process optimation. Beside and in addition to thermal analyses and optical methods electrical methods can be used, which depend on measuring of those electric properties, which are connected with each change of phases of the material under test. By use of potentials of medium or high frequency the cell of reaction is free of test probes. This is especially favourable for investigations of such mixtures of phases, in which the surfaces of electrodes would be changed irreversible by sedimentation or separation of phase. In this way the following reactions were studied: precipitation processes in supersaturated aqueous solutions, solution of crystals of potassium chloride, adsorption of alkali solution by ground quartz, sedimentation of mineral substances, separation processes of the system phenol-water and transformation of high polymers.     

Preparation and partial characterization of a soluble site-to-site directed enzyme complex composed of alcohol dehydrogenase and lactate dehydrogenase

A soluble, bifunctional enzyme complex has been prepared by crosslinking lactate dehydrogenase and alcohol dehydrogenase with glutaraldehyde. The crosslinking was performed on a solid phase while the active sites of alcohol dehydrogenase and lactate dehydrogenase were held adjacent to one another with the aid of a bis-NAD analog. Subsequently, the enzyme complex was released from the solid phase. The soluble enzyme complex was then purified by using NAD-Sepharose as an affinity adsorbent. Based on gel filtration experiments, the complex was estimated to consist of one of each dehydrogenase. By using a third enzyme, lipoamide dehydrogenase, which competes with lactate dehydrogenase for NADH produced by alcohol dehydrogenase, the effect of site-to-site orientation was studied. It was found that about 83% of the NADH produced by alcohol dehydrogenase was oxidized by site-to-site oriented lactate dehydrogenase compared to a figure of only about 61% obtained in an identical system of separate enzymes. This indicates that given two alternative routes, the preference for the one to lactate dehydrogenase over the one to lipoamide dehydrogenase is enhanced when lactate dehydrogenase and alcohol dehydrogenase are site-to-site oriented.     

Correlation energy extrapolation by intrinsic scaling. III. Compact wave functions

The information gained in the context of extrapolating the correlation energy by intrinsic scaling is used to shorten the full configurational expansions of electronic wave function without compromising their chemical accuracy. The truncations are accomplished by judiciously limiting the participation of the ranges of predetermined approximate sets of natural orbitals in the various excitation categories.     

Studying lateral diffusion in lipid bilayers by combining a magic angle spinning NMR probe with a microimaging gradient system

An alternative technique for studying the lateral diffusion in lipid membranes using pulsed field gradients in combination with magic angle spinning is presented. It is shown that MAS probes inserted in a microimaging device that produce high field gradients can be used to monitor also slow diffusion processes. As an example, measurements of the lateral diffusion of lipids embedded in the bilayer of a cubic phase are presented.     

New stationary phases of conjugated π-electron systems for HPLC—characterization of structure and dynamics by solid state NMR spectroscopy

Four new stationary phases for HPLC were prepared by modifying silica gel with a trifrnctional aminoalkyl silane. A conjugated π-electron system was linked to the amino group either directly or with a carboxylic anhydride as a spacer in between. Characterization and dynamic measurements of the new stationary phases were performed by solid state NMR spectroscopy. The results of the ²⁹si and ¹³C CP/MAS techniques were compared with the recently developed ¹H MAS-only technique. Despite strong homonuclear dipole-dipole interactions it was possible to obtain well resolved ¹H MAS spectra of those stationaru phases with a high degree of crosslinking. Limited mobility of the aromatic ligand fragments is common for all examined stationaryu phases. The chromatographic properties of the new phases were tested by their ability tio sepatate a mixture of eight PAHS. It could be shown that the π-π interaction mechanism is responsible for the separation of the eight PAHs, because the elution order of the PAHs did not changem despite the use of both a nonpolar mobile phase (n-heptane) and a polar mobile phase (methanol/ water mixture).     

Syntheses of Anthracenones. 1. Sodium Dithionite Reduction of peri-Substituted Anthracenediones

The reaction of peri-substituted anthracenediones with sodium dithionite in dimethylformamide and water has been investigated. The system selectively reduces the carbonyl group flanked by the peri substituents of the anthracenediones to give the corresponding 4,5-disubstituted 9(10H)-anthracenones and thus provides a route to anthracenones which are otherwise difficult to obtain. Many functional groups can be tolerated, the reaction is compatible with the presence of peri alkoxy groups and unsaturated side chains of the starting anthracenediones, and the reduction does not go beyond the anthracenone stage. However, the formation of anthracenones depends on the nature of the peri substituents. No products were obtained from the 1,8-dimethyl-substituted anthracenedione and the parent compound with no substituents.     

Synthetic Cu0.507(5)Pb8.73(9)Sb8.15(8)I1.6S20.0(2) nanowires

Nanowires of an iodine containing Pb-Sb-sulfosalt have been synthesized by chemical vapor transport. Their structure was studied using high-resolution transmission electron microscopy and X-ray powder diffraction. The lattice parameters show values equal to a=4.9801(4) nm, b=0.41132(8) nm (with two-fold superstructure), c=2.1989(1) nm and β=99.918(6)°. These parameters and the results of a multislice simulation are in good agreement with the mineral pillaite, Cu_0.10Pb_9.16Sb_9.84S_22.94Cl_1.06O_0.5 (space group C2/m, a=4.949(1) nm, b=0.41259(8) nm, c=2.1828(4) nm, and β=99.62(3)°). Microprobe and EDX analyses yielded a chemical composition of Cu_0.507(5)Pb_8.73(9)Sb_8.15(8)I_1.6S_20.0(2) which is close to natural pillaite but contains no oxygen and iodine instead of chlorine. The structure of the investigated material is based on chains of M-S polyhedra (M=Pb or Sb) typical for the architecture of sulfosalts implying iodine atoms in trigonal prismatic coordination with Pb atoms from the M-S polyhedra of neighboring chains. The [010] superstructure of the specimen was found to be unstable under electron beam irradiation with a rapid decrease of the b lattice parameter from 0.8 to 0.4 nm within 5 min.