Radiation reduction of Cr, Mo and W isopolymetalates in aqueous system

The radiation-chemical processes in aqueous solutions of dichromates, isopolymolybdates and isopolytungstates have been studied. The radiation reduction of Cr(VI) to Cr(III), Mo(VI) to Mo(V) and W(VI) to W(V) takes place. Molybdenum and tungsten blues are the products of the last two processes in acid solutions. The yields of reduction decrease significantly with the increase of pH. The mechanisms of the processes have been discussed. The photochemical reduction of Mo(VI) and W(VI) for the production of corresponding 5-valent states have been used to the study of their electron scavenging efficiencies. It has been shown that these efficiencies decrease in the order: Mo(V)>W(V)>Cr(VI)>Mo(VI)>W(VI).     

The First Reaction of Dimethoxycarbene with an Imine Moiety

The nucleophilic dimethoxycarbene (DMC; 2 ) generated by thermal decomposition of 2,5‐dihydro‐1,3,4‐oxadiazole derivative 1 in boiling toluene reacts smoothly with N‐(9H‐fluoren‐9‐ylidene)‐4‐methylbenzenesulfonamide ( 7b ) to yield carbonimidoate derivative 10 . A multi‐step reaction pathway, initiated by the attack of DMC onto the C?N bond and followed by the migration of the sulfonyl group (or via a sulfinate anion) is proposed to explain the formation of the final product. In contrast to the formal ketimine 7b , N‐benzylidene‐4‐methylbenzenesulfonamide ( 7a ), a formal aldimine, does not react with DMC under comparable conditions.     

Separation of four platinum metals by anion-exchange in hydrobromic acid medium

Distribution coefficients of Pt, Ir, Pd and Rh in the systems Dowex 1 [Br^?]?HBr plus 0.0035M bromine and Dowex 1 [Br^?]?HBr plus 2% N₂H₄·HCl, were determined with the aid of radioactive tracers by batch equilibration for the resins of nominal cross-linking 2, 4 and 8, respectively. Column experiments showed that Dowex 1X4 should be used for separations because of the favourable dynamics of the column process. Elution conditions for the quantitative separation of both trace and milligram amounts of Ir?Pt, Rh?Pt, Pd?Pt and Ir?Pd?Pt mixtures are given. Some data on the effect of temperature upon the quality of separation are also presented.     

Monitoring of the metal displacement from the recombinant mouse liver metallothionein Zn(7)-complex by capillary zone electrophoresis with electrospray MS detection

A solution of a Zn-complex of recombinant mouse MT-1 isoform (Zn(7)-MT-1) was prepared and titrated with Cd(2+) ions. A method based on the coupling of capillary zone electrophoresis (CZE) with electrospray MS detection was developed for the analysis of the stoichiometry of the species formed during the titration. The method offered the possibility of the on-line removal of up to 100 mM Tris or phosphate buffer solutions that would otherwise suppress the electrospray signal. By allowing the determination of the metal stoichiometry of the complex species present in solution the method was shown to be complementary to circular dichroism and UV-VIS spectrophotometry conventionally used for similar studies. The titration of the Zn(7)-MT complex with Cd(II) showed the sequential displacement of the Zn by Cd. The unusually high stability of the Cd(6)Zn(1)-MT species was observed which suggests a structural role of the remaining Zn(II) ion.     

Studies on the copolymerization of unsaturated 1,3-dioxane derivatives—IV. Radical copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride

The copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride in the presence of a radical catalyst yields equimolar, alternating copolymers in which the furyl units have 2,5-linkage. It has been shown that 2-furyl-5,5-dimethyl-1,3-dioxane forms a charge transfer complex with maleic anhydride. The equilibrium constant for the complex was determined by NMR spectroscopy.     

Investigation of arsenic speciation in oyster test reference material by multidimensional HPLC-ICP-MS and electrospray tandem mass spectrometry (ES-MS-MS)

Multidimensional (size-exclusion-anion-exchange-cation-exchange) liquid chromatography with ICP-MS detection was developed to produce a map of water-soluble species in an oyster test reference material. The presence of arsenobetaine, trimethyl(2-carboxyethyl)arsonium inner salt, arsenocholine, dimethylarsonic acid, tetramethylammonium ion, As(v) and two arsenosugars was demonstrated by ES-MS-MS. A previously unreported compound was isolated and identified by ES-MS-MS as 5-dimethylarsinoyl-beta-ribofuranose. Anion-exchange chromatography was optimized to produce a chromatographically pure peak of arsenobetaine (accounting for ca. 64% of all water-soluble As present) that was used to quantify this compound.     

Thermochemical aspects of proton transfer in the gas phase

The beginning of the twentieth century saw the development of new theories of acidity and basicity, which are currently well accepted. The thermochemistry of proton transfer in the absence of solvent attracted much interest during this period, because of the fundamental importance of the process. Nevertheless, before the 1950s, few data were available, either from lattice energy evaluations or from calculations using the emerging molecular orbital theory. Advances in mass spectrometry during the last 40 years allowed studies of numerous systems with better accuracy. Thousands of accurate gas-phase acidities or basicities are now available, for simple atomic and molecular systems and for large biomolecules. The intrinsic effect of structure on the Br?nsted basic or acidic properties of molecules and the influence of solvents have been unravelled. In this tutorial, the basics of the thermodynamic principles involved are given, and the mass spectrometric techniques are briefly reviewed. Advances in the design and measurements of gas-phase superacids and superbases are described. Recent studies concerning biomolecules are also evoked.     

Structure of colloid silica determined by viscosity measurements

The viscosity of nanosized colloid silica suspensions, used as binders in the investment casting, was determined as a function of their weight fraction reaching 52%. A new capillary viscometer was used whose construction eliminated sedimentation effects. The experiments have been carried out at fixed pH 10.0 and controlled ionic strength. It was found that for a low silica concentration range (weight fraction below 5%) the suspension viscosity increased more rapidly than the Einstein theory predicts. This anomalous behavior could not be explained in terms of the primary electroviscous effect predicted to be a few orders of magnitude smaller as observed. This discrepancy was accounted for by postulating a fuzzy, gel-like structure of colloid silicas used in our experiments. Hence, the apparent hydrodynamic radius of silica particles in aqueous suspensions was found to be larger than the primary particle size in accordance with previous observations. Based on this postulate, an apparent density of the silica sols was found to be 1.32-1.37 g/cm(3) instead of 2.2-2.32 g/cm(3) as determined from the suspension dilution method. This behavior was interpreted in terms of the core/shell model with high shell porosity, reaching 85%. Similarly, for higher concentration ranges, silica viscosity increased more rapidly with increased sol concentration than predicted by the Batchelor model derived for hard particles. The deviation was attributed to the secondary electroviscous effect stemming from the electrostatic interactions among silica particles in sheared suspensions. This effect has quantitatively been interpreted in terms of Russel's theory. On the other hand, for the high concentration range the experimental results were well accounted for by the Dougherty-Krieger model. By exploiting our experimental findings a sensitive method of determining the structure and apparent density of silica sols in aqueous media was proposed.     

Phosphomimetic sulfonamide and sulfonamidoxy analogues of (Lyso)phosphatidic acid

Lysophosphatidic acid (LPA) and phosphatidic acid (PA) are potent bioactive lipid mediators of signal transduction and are inactivated by phosphatases. To obtain receptor-isoform selective ligands with neutral phosphomimetic head groups, we performed the stereoselective synthesis of LPA and PA analogues with trifluoromethanesulfonamide and trifluoromethanesulfonamidoxy moieties replacing the phosphomonoester.     

Nucleophilic substitution of hydrogen in meso-nitroaryl-substituted porphyrins—unprotected at the NH-centers in the core ring

Unprotected 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and 5,10-bis(4-nitrophenyl)-15,20-diphenylporphyrin react in the presence of a base at low temperature with carbanions (which bear a leaving group X at the carbanionic center) affording vicarious nucleophilic substitution of hydrogen (VNS) products in good yields (50-89%). The reactivity is explained in terms of the predominance of the porphyrin N-anion resonance forms at this temperature.