Herstellung von 1-Aminoalkan-1,1-diphosphonsäuren

1-Aminoalkane-1,1-diphosphonic acids 1 , 2 or 3 are formed in the reaction of carboxylic acid amide dihalides or carboxylic acid amide hydrohalogenides with phosphorous acid. Phosphorus trihalides plus water may be used in lieu of phosphorous acid in the reaction with carboxylic acid amides. With formamide either aminomethanediphosphonic acid ( 1a ) or 2-oxo-2-hydroxy-5-amino-1,4,2-oxazaphospholidine-3-phosphonic acid ( 5 ) are obtained depending on the reaction conditions.     

Infrared study of the adsorption of hydroxycarboxylic acids onα-FeOOH and amorphous Fe (III)hydroxide

Summary The adsorption of lactic acid, meso-tartaric acid,l-tartaric acid and citric acid on-FeOOH and amorphous Fe(III)hydroxide was investigated by i.r. spectroscopy. The results indicate that adsorption is based on partial replacement of the surface hydroxyl groups by carboxylate groups. For meso-tartaric acid on-FeOOH and for lactic acid andl-tartaric acid on amorphous Fe(III)hydroxide deprotonated alcoholic hydroxyl groups participate in the surface complex formation. A tentative model for the adsorption on the (100) face of-FeOOH is presented.

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Zusammenfassung Die Adsorption von Milchsäure, meso-Weinsäure,l-Wein-säure und Citronensäure an-FeOOH und amorphem Fe(III)hydroxid wurde mit Hilfe von Infrarotspektroskopie untersucht. Die Ergebnisse zeigen, daß die Adsorption zu Oberflächenkomplexen führt, wobei die grenzflächenständigen Hydroxylgruppen der adsorbierenden Feststoffe teilweise durch Carboxylatgruppen ersetzt werden. Bei der Adsorption von meso-Weinsäuren an-FeOOH bzw. Milchsäure und l-Weinsäure an amorphem Fe(III)hydroxid sind zusätzlich deprotonierte alkoholische Hydroxylgruppen an der Komplexbildung beteiligt. Ein provisorisches Modell beschreibt die Anordnung der Liganden auf der (100)-Fläche von-FeOOH.

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With 2 figures and 3 tables     

A study of some parameters relevant to the response of harwell PMMA dosimeters to gamma and electron irradiation

The effects on the radiation response of Harwell polymethylmethacrylate (PMMA) dosimeters of dose-rate, radiation type, temperature during irradiation and post-irradiation storage, and post-irradiation stability, are of importance to the operators of commercial irradiation facilities.

This paper describes recent studies of the effects of some of these parameters on the radiation response of Harwell Red 4034, Amber 3042, and Gammachrome YR Perspex dosimeters, and provides data on batch to batch variation and shelf-life.     

Mass spectrometric characterization of stathmin isoforms separated by 2D PAGE

In proteome analysis, the determination of the phosphorylation status of proteins and protein isoforms, which have been separated by two-dimensional polyacrylamide gel electrophoresis (2D PAGE), is of prime importance in addition to their identification. In this study, the extent to which such information can be directly extracted from the mass spectrometric data used for identification was evaluated. By searching for metastable peaks which are characteristic for loss of phosphoric acid, the Ser-phosphorylated peptides were identified with a high success rate in reflector matrix-assisted laser desorption/ionization (MALDI) mass maps of in-gel digested proteins. Furthermore, by employing a double enzymatic strategy using trypsin and Glu-C in parallel, improved sequence coverage and additional separation of the potential phosphorylation sites of the isoforms were achieved. The precise location of the modified sites within an identified phosphopeptide was obtained by submitting the corresponding molecular ions directly to nano-electrospray tandem mass spectrometric analysis. In this way the detailed phosphorylation status of six isomers of stathmin separated by 2D PAGE was determined. Two of these six isomers were phosphorylated at all four known sites (serines 15, 24, 37 and 62) and were probably derived from the previously reported alpha and beta forms, which differ by a yet unknown modification. In addition, isomers phosphorylated at serines 15, 24 and 37, serines 24, 37 and 62, serines 24 and 37 and serine 37 only were characterized.     

Representations of state space transformations by Markov kernels

Every convex subset of a locally convex Hausdorff space (X, ) is equipped with the (-algebra generated by its-relatively open subsets. Within the set () of probability measures on two particular convex subsets are considered: (a) the set ^s () of probability measures with a separable support, and (b) the set ^c () of probability measures with a compact convex support. If is the base of a cone inX, then there exists an affine barycenter map from ^c () onto whose composition with the natural embedding of in ^c () yields the identity map on , and every-continuous affine transformation of can be represented by an affine transformation of ^c () that is induced by a Markov kernel. If (X, ) is a Banach space and is a closed, bounded, generating cone base inX that is contained in a hyperplane, then analogous results are obtained with respect to ^s (). Since the state spaces considered in noncommutative measure theory are cone bases and every change in time of an empirical system can be thought of as an affine transformation of the associated state space (Schrödinger picture), the existence of these representation theorems implies that the time evolution of general empirical systems can be described by dynamical concepts borrowed from classical probability theory.     

Siloxane Compounds of the Transition Metals

Heterosiloxanes of transition metals contain the characteristic grouping Si? O? X; in the compounds known so far, X may be Au, Zn, Cd, Hg, Ti, Zr, Hf, V, Nb, Ta, Cr, U, Re, Fe, Co, Ni, or Pt. Most of these compounds are obtained from silanols, metal silanolates, acyloxysilanes, disiloxanes, or alkoxysilanes, i.e. from compounds that already contain an Si? O bond. The transition metal may be introduced e.g. as a halide, as an organometailic compound, as an alkoxy compound, or as an oxide. Heterosiloxanes are also formed on reaction of many silicon compounds that do not contain oxygen with transition metal compounds containing oxygen. Some of these compounds, e.g. some titanosiloxanes, are very stable, whereas others decompose explosively. Oligomeric and polymeric heterosiloxanes exist in addition to the monomeric compounds.     

Halogenation reactions in position 3 of quinoline-2,4-dione systems by electrophilic substitution and halogen exchange

Summary 3-Substituted 4-hydroxy-2(1H)-quinolones3,5,7 are halogenated with bromine or sulfuryl chloride to yield the quinolinediones9 or10. Reaction of3,5,7 with chloroform gives the dichloromethyl quinolinediones11. Halogen exchange leads from the chloro quinolinediones10 to fluoro quinolinedones12 and to azido quinolinediones13. Similarly the dichloro quinolinedione10 an reacts to the difluoro quinolinedione14, which is reduced to the 3-fluoro-4-hydroxyquinolone16 and reacts again with sulfuryl chloride to give the mixed 3-chloro-3-fluoroquinolinedione15.Herrn Prof. Dr. Erich Ziegler in freundschaftlicher Verbundenheit zum 80. Geburtstag gewidmet.     

Zur Thermodynamik der Metallcarbonate. 2. Mitteilung [1]. Löslichkeitskonstanten und Freie Bildungsenthalpien von Cu2(OH)2CO3 (Malachit) und Cu3(OH)2(CO3)2 (Azurit) bei 25°C

The solubilities of Cu₂(OH)₂CO₃ (malachite) and Cu₃(OH)₂(CO₃)₂ (azurite) have been studied at 25° C in solutions of the constant ionic strength 0,2 M consisting primarily of sodium perchlorate. From experimental data the following values for equilibrium constants and Gibbs energies of formation are deduced: Predominance area diagrams for the ternary system Cu²⁺ H₂O-CO_2(g), including CuO, Cu(OH)₂, Cu₂(OH)₂CO₃, Cu₃(OH)₂(CO₃)₂, Cu²⁺ and Cu (CO₃)₂²⁻, are given.