Computation of LCAO wave functions for ground states of polymers and solids

The LCAO form of the Hartree–Fock method is discussed in its application to crystals. General formulae are given for obtaining Fourier coefficient of electronic density (in direct space) as well as of the band structure (in momentum space). Finally, it is shown that in its LCAO form, Slater–Hartree–Fock equations are very simple and that this method is of interest for numerical applications. Special integrals occurring in this formalism are evaluated for a Gaussian basis in the last part of this paper.     

Determination of 2-mercaptopropionylglycine and its metabolite, 2-mercaptopropionic acid, in plasma by ion-pair reversed-phase high-performance liquid chromatography with post-column derivatization.

A simple and fast high-performance liquid chromatographic method was developed for the simultaneous measurement of 2-mercaptopropionylglycine (Tiopronine) and its metabolite (2-mercaptopropionic acid) in human plasma after the administration of a pharmaceutical dosage form (Acadione). The sample treatment before high-performance liquid chromatographic analysis consisted of the reduction of the corresponding disulphides by tri-n-butylphosphine and protein precipitation with ethanol. Separation was achieved by ion-pair high-performance liquid chromatography on a reversed-phase column (LiChrospher RP 18e) with cetrimonium bromide as counter ion and detection by fluorimetry after post-column derivatization with a selective thiol reagent, i.e. pyrenemaleimide. The high frequency of the analyzed samples and validation results make the method suitable for pharmacokinetic studies, and this was demonstrated by the first results obtained after the administration of an oral dose of 500 mg of Tiopronine to two healthy subjects.     

Dynamical systems theory for music dynamics

We show that, when music pieces are cast in the form of time series of pitch variations, the concepts and tools of dynamical systems theory can be applied to the analysis of temporal dynamics in music. (i) Phase space portraits are constructed from the time series wherefrom the dimensionality is evaluated as a measure of the global dynamics of each piece. (ii) Spectral analysis of the time series yields power spectra ( approximately f(-nu)) close to red noise (nu approximately 2) in the low frequency range. (iii) We define an information entropy which provides a measure of the local dynamics in the musical piece; the entropy can be interpreted as an evaluation of the degree of complexity in the music, but there is no evidence of an analytical relation between local and global dynamics. These findings are based on computations performed on eighty sequences sampled in the music literature from the 18th to the 20th century. (c) 1995 American Institute of Physics.     

Condensation du complexe hexafluoroacetone - fluorure de potassium sur les cetones alpha - halogenees

During its condensation with α-halo ketones, the hexafluoro- acetone-potassium fluoride complex behaves as a weak nucleophile and a strong base. Nucleophilic substitution produces α-perfluoroalkoxy ketones. Abstraction of a proton α to the carbonyl function leads to the formation of ether-ketones substituted by the group C(CF₃)₂. In some cases, hydrogen halide elimination can occur.     

Note sur le mécanisme réactionnel de la transposition de Dimroth. Une étude ab initio

An ab initio study of the Dimorth rerarrangement of the -amino-1,2,3,4-tetrazole leads to the conclusion teht in vapour phase the rate determining step is not the ring-chain isomerism, but is either the Z-E iomerism around the C?N double bond or the 1,3-sigmatropic shift of the proton.     

SPECTROCSOPIC STUDIES OF PURINES—III. PROPERTIES OF PURINES SUBSTITUTED AT THE SIXTH AND NINTH POSITIONS*

Abstract— We have investigated the effects of solvent and pH on the absorption and emission propertied of various 6- and 9-substituted purines as a means of examining the nature of the directed not only at deteriming the relative energies of (π,π*) and (π,π*) states, but in particular, at examining the nature and energies of the two lowest-lying (π,π*) states. For examplem, the attachment of a methyl or ribosyl group to the N9 of purine does not change the relative energies of the lowest-lying (π,π*) and (π,π*) states; thus, the latter is the singlet of lowest energy. However, the lowest singles in derivatives formed by substitution at C6 are(π,π*) states—i.e. there is no long-wavelength tail in the absorption spectra and florescence is comparable in intensity to phosphorescence. Further the absence of emission from neutaral adenine at room temperature is due to temperature quenching. Both lowest (π–π*) transtions. are contained under a common envelope and cannot be resolved in the absorption spectra. The shoulder observed in some of these compounds on the long-wavelength slope of absorption envelope is vibrational in nature. Consideration of the effects of solvents on absorption and the analysis of luminescence spectra make it possible to locate the relative position of these (π–π*) transitions within the common envelope. In compounds with an -H on N9 and a free (aza) N1 (e.g. adenine, anionic hupoxanthine) the weaker, solvent-sensitive (W) band has a higher energy then the more intense, solvent-insensitive (S) band. When N1 is protonated, (e.g., in hypoxanthine or cationic adenine) and/or when methyl or ribosyl is substituted at N9, the order of these bands is inverted due ot a red shift of the W band. This shift is most apparent in the 9-substituted hypoxanthines, where in non-polar solvents the W band can be readily resolved in the absoption spectra. This inversion results in a red shift of both fluorescence and phophorescence and an increase of the P/F ratio. When chlorine or iodine is attached at C6 only phosphorescence having a very short lifetime appears due to heavy atom enhancement of single—triplet transitions.     

Investigation of U(VI) extraction with calixarene: Application to analysis of urine sample

A macrocyclic molecule, the calix[6]arene 4₆, functionalized with carboxy groups, has been studied and its extraction efficiency towards uranium determined in a two phases solvent-extraction system. Two solvents, dichloromethane and benzene were used to follow uranium extraction from media containing sodium ions. The study of the extraction parameters allowed proposing an extraction scheme with each solvent. The extraction efficiency was found to increase with pH, with an optimal efficiency of nearly 100%. No decrease of uranium extraction was observed in synthetic solutions containing sodium ions (spiked with²²Na) and/or²³⁹Pu. Under specific conditions, almost 100% of uranium have been extracted by the calixarene from real urine samples.     

Bestimmung von Metallspuren in Polymeren mit Hilfe der Atom-Absorptionsspektrophotometrie

Zusammenfassung Die Atom-Absorptionsspektrophotometrie erlaubt die schnelle und genaue Bestimmung von Metallen in Polymeren, und zwar sowohl im ppm- als auch im Prozentbereich. Bei löslichen Polymeren werden vorzugsweise 2%ige Lösungen untersucht. Polymere, die in keinem geeigneten Lösungsmittel löslich sind, werden mit H₂SO₄/H₂O₂ aufgeschlossen. für flüchtige Metallverbindungen wird eine Umfällmethode mit anschließender Anreicherung der Metallspuren beschrieben. Untersucht werden Polystyrol, Celluloseester, Polyacrylnitril, ABS-Polymere, Polycarbonat, Polyvinylchlorid und seine Copolymeren, Polyamid, Polyäther, Wolle und Baumwolle. Nachweisgrenzen und günstigste Konzentrationsbereiche für die Elemente Li, Na, K, Mg, Ca, B, Al, Si, Sn, Pb, Sb, Cu, Ag, Au, Zn, Cd, Hg, Ti, Fe und Ni werden angegeben.

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Determination of trace metals in polymers by atomic absorption spectrophotometry

Atomic absorption spectrophotometry allows quick and exact determination of both ppm and percent quantities of metals in polymers. Preferably 2% solutions of soluble polymers are analyzed. Polymers insoluble in a suitable solvent are ashed in H₂SO₄/H₂O₂. For volatile metal compounds a double precipitating method followed by enrichment of trace metals is described. The following polymers are studied: polystyrene, cellulose esters, polyacrylonitrile, acrylonitrile-butadiene-styrene-terpolymers, polycarbonate, Polyvinylchloride and its copolymers, polyamide, polyether, wool, and cotton. Detection limits and most favourable concentration ranges are reported for the elements Li, Na, K, Mg, Ca, B, Al, Si, Sn, Pb, Sb, Cu, Ag, Au, Zn, Cd, Hg, Ti, Fe, and Ni.

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Herrn Prof. Dr. K. Hansen zum 60. Geburtstag gewidmet.

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An dieser Stelle sei Herrn Dr. A. Reichle, dem Leiter des Wissenschaftlichen Laboratoriums der Farbenfabriken Bayer AG, Werk Dormagen, für seine Unterstützung gedankt.Den Herren K. Schumann und W. Kremer danke ich für ihre sorgfältige experimentelle Mitarbeit.