Zur Kenntnis der Verbindung H3P–BJ3

Phosphine or phosphonium iodide react with boron triiodide in CS₂ or benzene to form the adduct H₃P–BI₃. The water-sensitive white solid is thermally stable up to ～150°C. Its IR and NMR spectrum are recorded.     

Comparison of figures of merit for fluorimetric analysis of rhodamine complexes of gallium and indium by excitation with pulsed laser and by xenon arc sources

Optimum conditions have been established for formation and extraction of indium-Rhodamine complexes, and limits of detection found for fluorimetric determination of gallium and indium by means of Rhodamine dyes, using the excitation with pulsed laser and xenon arc sources.     

A complexometric titration of inorganic sulphate in synthetic detergents

An accurate method for the determination of inorganic sulphate in synthetic detergents has been developed. After addition of a cationic surface-active agent (cetyl pyridinium chloride) to an anionic detergent, sulphate can be determined by means of indirect titration with EDTA, using a mixture of Metalphthalein and Naphthol Green B as indicator.     

Derivatization of carboxylic acids with 9-bromomethylacridine using micellar phase-transfer catalysis

Summary Micellar phase-transfer catalysis (MPTC) offers the opportunity to derivatize carboxylic acids directly in an aqueous matrix without prior extraction of the acids into a suitable aprotic solvent. The currently developed MPTC system consists of a non-ionic surfactant, Arkopal N-130, an ion-pair agent, tetrakis-(decyl)-ammonium bromide, and a novel fluorescence reagent, 9-bromomethylacridine. The MPTC system can be applied to the derivatization of many types of carboxylic acids. The reaction rate is affected by the lipophilicity of the acid and by the presence of other functional groups. For lipophilic carboxylic acids the reaction is complete within 5 min at 60°C and pH 7.0.     

Conformation and chiroptical properties of mandelic acids

Using CD data (solution, solid state, various temperatures), X-ray data and MO calculations for a number of substituted mandelic acids (phenylglycolic acids) an attempt was made to explain the different results for the relation between sign of the ¹L_b CD band and substitution pattern as described in the literature for various types of aromatic compounds. Moreover the reported sector rule has been reconsidered taking into account the sign and magnitude of the spectroscopic moments. It has been found that in any explanation of the signs of the ¹L_b CD bands of substituted aromatic compounds both the conformational behaviour and the spectroscopic moments should be taken into account.     

Enhanced selectivity in Novozym 435 catalyzed kinetic resolution of secondary alcohols and butanoates caused by the (R)-alcohols

In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced.     

Two-state irreversible thermal denaturation of anionic peanut (Arachis hypogaea L.) peroxidase

Detailed differential scanning calorimetry (DSC), steady-state tryptophan fluorescence and far-UV circular dichroism (CD) studies, together with enzymatic assays, were carried out to monitor the thermal stability of anionic peanut peroxidase (aPrx) at pH 3.0. The spectral parameters were seen to be good complements to the highly sensitive but integral method of DSC. Thus, changes in far-UV CD corresponded to changes in the overall secondary structure of the enzyme, while changes in intrinsic tryptophan fluorescence emission corresponded to changes in the tertiary structure of the enzyme. The results, supported with data concerning changes in enzymatic activity with temperature, show that thermally induced transitions for aPrx are irreversible and strongly dependent upon the scan rate, suggesting that denaturation is under kinetic control. It is shown that the process of aPrx denaturation can be interpreted with sufficient accuracy in terms of the simple kinetic scheme, , where k is a first-order kinetic constant that changes with temperature, as given by the Arrhenius equation; N is the native state, and D is the denatured state. On the basis of this model, the parameters of the Arrhenius equation were calculated.     

Sorption of caesium and strontium on clinoptilolite-and mordenite-containing sedimentary rocks

The sorption of caesium and strontium from its aqueous solutions by ten clinoptilolite-and mordenite-containing sedimentary materials from Slovakia, Bulgaria, Ukraine and Greece was investigated by batch-type procedure and radiotracer techniques. The concentration of the solutions, that were performed in and without the presence of competing cations (0.005 mol·dm⁻³ KCl) varied between 1·10⁻⁴ and 5·10⁻² mol·dm⁻³. The uptake and distribution coefficient (K _d ) values determined for the materials of the different origin, were correlated with their mineralogical composition and gross cation exchange capacity (CEC). The identification of the specific uptake sites was attempted on the basis of the sorption isotherms and the content of exchangeable cations. The experimental results provide information on the suitability of the individual materials for the treatment of radioactive wastes and their application as backfills in potential nuclear waste repositories.     

Cover Picture

The cover picture shows the structure, determined crystallographically, of the tetrakis(trimethylstannyl)phosphonium cation that is formed with surprising ease from the reaction of P(SnMe(3))(3) with Me(3)SnOTf (OTf=OSO(2)CF(3)) and is isolated as the OTf salt. It is the first completely substituted main group organometallic phosphonium derivative, and, in contrast to the more common tetraorganic-substituted phosphonium cations is only stable in the solid state; in solution it functions as a masked Me(3)Sn(+) reagent. More about this chameleonlike ion and the N(SnMe(3))(4) cation homologue, which is equally dynamic in solution and has unusual long Sn-N bond lengths, is reported by M. Driess et al. on p. 3684 ff.