Design,synthesis, and evaluation of 6-carboxyalkyl and 6-phosphonoxyalkyl derivatives of 7-oxo-8-ribitylaminolumazines as inhibitors of riboflavin synthase and lumazine synthase

A series of 6-carboxyalkyl and 6-phosphonoxyalkyl derivatives of 7-oxo-8-D-ribityllumazine were synthesized as inhibitors of both Escherichia coli riboflavin synthase and Bacillus subtilis lumazine synthase. The compounds were designed to bind to both the ribitylpurine binding site and the phosphate binding site of lumazine synthase. In the carboxyalkyl series, maximum activity against both enzymes was observed with the 3'-carboxypropyl compound 22. Lengthening or shortening the chain linking the carboxyl group to the lumazine by one carbon resulted in decreased activity. In the phosphonoxyalkyl series, the 3'-phosphonoxypropyl compound 33 was more potent than the 4'-phosphonoxybutyl derivative 39 against lumazine synthase, but it was less potent against riboflavin synthase. Molecular modeling suggested that the terminal carboxyl group of 6-(3'-carboxypropyl)-7-oxo-8-D-ribityllumazine (22) may bind to the side chains of Arg127 and Lys135 of the enzyme. A hypothetical molecular model was also constructed for the binding of 6-(2'-carboxyethyl)-7-oxolumazine (15) in the active site of E. coli riboflavin synthase, which demonstrated that the active site could readily accommodate two molecules of the inhibitor.     

Self-Assembly of Gold Nanoclusters on Molecularly Modified GaAs

The elaboration of closed-packed monolayers of Au₅₅(PPh₃)₁₂Cl₆ clusters on oxidized and non-oxidized GaAs surfaces is reported. The first part of this work describes the use of silanethiol modified GaAs oxide surfaces to trap 18 nm gold colloids and Au₅₅(PPh₃)₁₂Cl₆ clusters. The surfaces characterized by AFM measurements present high-quality coverage on a quite long range for both metallic species. The second part is devoted to the elaboration of Au₅₅(PPh₃)₁₂Cl₆ cluster monolayers on non-oxidized p-type GaAs substrates, functionalized with dithiol molecules. AFM measurements demonstrate the presence of closed-packed two-dimensional arrangements of Au₅₅ clusters.     

Semi-preparative liquid-chromatographic separation of all four stereoisomers of α-bisabolol on tribenzoylcellulose

Summary A semi-preparative low-pressure liquid-chromatographic procedure using tribenzoylcellulose has been developed for the separation and isolation of the four -bisabolol stereoisomers. Stereochemical assignments were made by HPLC-polarimeter coupling and by using the authentical isomers. This method can be applied to the quality control of chamomile preparations, as it allows the detection of adulterations resulting from admixtures of synthetic -bisabolol. In addition, the isolation of all four -bisabolol stereoisomers from commercially available synthetic -bisabolol has been made possible.     

Mitteilungen aus dem Institut für Radiumforschung

Zusammenfassung Es wurde mit Hilfe des schon früher beschriebenen Quarzapparates Thoriumbromid aus reinem Thoroxyd dargestellt, das nach zwei verschiedenen Methoden gereinigt war und auf Grund spektroskopischer Untersuchung als absolut rein und frei von seltenen Erden angesehen werden mu\te.Das geschmolzene Thorbromid wurde nach zwei Methoden analysiert und dabei die beiden VerhÄltnisse ThBr₄4 Ag und ThBr₄4 AgBr bestimmt.Zwei unabhÄngige Serien von 12, respektive 15 Analysen gaben die folgenden Resultate:Serie I. 54·45867g Thorbromid verbrauchten 42·58666g Silber und gaben 74·13448g Silberbromid, entsprechend einem Atomgewicht des Thoriums Th=232·15±0·016.Serie II. 74·30630g Thorbromid verbrauchten 58·11096g Silber und gaben 101·15848g Silberbromid, woraus sich das Atomgewicht Th=232·12±0·014 berechnet.Als Mittel dieser beiden Werte ergibt sich Th=232·135.Da aber die Analysenserie aus den oben besprochenen, uns triftig erscheinenden Gründen als die zuverlÄssigere angesehen werden mu\, glauben wir, da\ der aus ihr resultierende WertTh=232·12 als das derzeit wahrscheinlichste Atomgewicht des Thoriums anzusehen ist, wenn Ag=107·880 angenommen wird. Aus dem in 27 Bestimmungen gefundenen VerhÄltnis von angewandtem Silber zu gefundenem Silberbromid, AgAgBr= 0·574453, ergibt sich dann das Atomgewicht des Broms zu Br=79·916 in vollster übereinstimmung mit der von Baxter seinerzeit gefundenen Zahl.     

PHYTOCHROME and THE DEVELOPMENT OF PHOTOPHOSPHORYLATION CAPACITY—AN APPRAISAL OF THE EXPERIMENTAL APPROACH*

Abstract— Development of the capacity for photophosphorylation (= total capacity for light-driven ATP formation) in the mustard ( Sinapis alba L.) cotyledons is strongly influenced by a red light pulse pretreatment which operates through phytochrome. The present report deals with several objections raised against the in situ assay of the rate of photophosphorylation. Experimental evidence is given in support of the assumption that the linear increase of the ATP content of the cotyledons as measured over 1.5 min after the onset of saturating white light (370 Wm^-2) in fact represents the maximum rate of photophosphorylation ('capacity'). Moreover, it is confirmed that control by phytochrome of the development of the photophosphorylation capacity and of the capacity for chlorophyll synthesis are unrelated phenomena. The failure of development of the capacity for photophosphorylation in isolated cotyledons from dark-grown seedlings cannot be attributed to deficiencies of chlorophyll synthesis.
It is concluded that the photophosphorylation response is particularly useful to study the mechanism of phytochrome (P_fr) action in case of a response which involves a threshold reaction and an interorgan (hook→cotyledon) cooperation.     

Über einige neue Bispirane

We have obtained four new bispirane systems in which both spiroatoms are vicinal atoms in cyclopropane or cyclobutane rings and in which the heterocyclic component has the basic structure of 1,4-dioxep-2-ene. We have shown that from two possibilities (bispiran, propellan) the general reaction leads only to a bispiran system. To the bispiran2 exhibiting the highest hyperchromism we ascribed the bispirocoplanar conformation (Fig. 1).

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Identification of amber and imitations by near infrared reflection spectroscopy

Imitations of amber have been prepared since a long time, but the number of imitations is increasing since modern polymers are available. At present, many imitations are based on a few synthetic polymers and even experts have some problems in distinguishing between real and falsed amber without destruction of the material. IR-Spectroscopy or pyrolysis combined with gas chromatography/mass spectrometry are very efficient methods in identifying amber and imitations but these methods need a sample preparation. By means of near infrared reflection spectroscopy it is possible to identify amber and imitations without any sample preparation in a short time. Optimization of the method and the application are discussed.     

Classification of Poincaré duality algebras over the rationals

The Poincaré duality algebras over Q play a key role in the rational homotopy classification of closed manifolds [3]. In this paper we give a way of classifying general Poincaré duality algebras and then specialize to the case of algebras which are generated by some homogeneous component and show how the classification reduces to the linear classification of certain homogeneous polynomials and exterior forms.     

IBX-mediated alpha-hydroxylation of alpha-alkynyl carbonyl systems. A convenient method for the synthesis of tertiary alcohols

[reaction: see text] IBX (o-iodoxybenzoic acid) is an excellent reagent for the alpha-hydroxylation of alpha-alkynyl carbonyl compounds without giving dehydrogenation products. The convenient procedure proves to be useful for the construction of a variety of tertiary alcohols (55-91%) under mildly acidic conditions.