Effect of fulvic acid on neodymium uptake by goethite

Experimental studies of the interaction of aqueous neodymium (Nd), Suwannee River fulvic acid (FA), and solid phase goethite were conducted. Results from blank systems (individual Nd and FA), binary systems (Nd-goethite, FA-goethite, and Nd-FA), and ternary systems (Nd-FA-goethite) at 0.1 mol/kg and 25 °C are reported.In the binary Nd-goethite system a classic sorption edge is observed, whereby virtually all Nd is removed from solution above the goethite point of zero charge (PZC). Similarly, the binary FA-goethite system exhibits strong FA sorption; However in this system near complete removal of FA from solution is observed below the goethite PZC. In the binary Nd-FA system, both aqueous Nd and FA feature a sharp decrease in concentration at ca. pH 9.Various experiments in the ternary system were conducted. For all concentrations, FA enhanced Nd sorption below the goethite PZC, attributed to the formation of a Type B ternary surface complex (mineral-ligand-metal ion). Notably, the 100 ppm FA ternary system showed anomalously high dissolved Nd in solution above the PZC (i.e., Nd sorption suppression) and a concomitant increase in goethite dissolution (∼9 ppm total Fe³⁺ observed above circa pH 9.5).Our results suggest that Nd-FA complexation plays a key role in Nd uptake by goethite, and that this process is largely governed by pH: Whereas at pHs below the goethite PZC, Nd-FA complexation facilitates Nd sorption, above the PZC, and particularly at elevated FA concentrations, the formation of aqueous Nd-FA complexes suppresses Nd removal. Moreover, under these conditions, goethite dissolution may also play a role in mitigating Nd uptake by goethite.     

NMR studies on natural and synthetic Amavadin

The stereochemistry of isolated natural product Amavadin, which contains a 1:2 complex of V(IV) with N-hydroxyimino-2,2'-dipropionic acid (HIDPAH(3)), and some synthetic complexes have been investigated. Amavadin was isolated from Amanita muscaria and oxidized with [NH(4)](2)[Ce(NO(3))(6)]. H(2)[Delta-V(S,S-HIDPA)(2)].3H(2)O, H(2)[Delta,Lambda-V(S,S-HIDPA)(2)].3H(2)O and their equivalent oxidized species have been synthesized and characterized spectroscopically. A combination of COSY, NOE, (1)H, (13)C-NMR and CD spectroscopy have been used to prove that the isolated natural product Amavadin consists of an almost equal mixture of the Delta- and Lambda-isomers of [V(S,S-HIDPA)(2)](2-).     

Fast voltammetric studies of the kinetics and energetics of coupled electron-transfer reactions in proteins

A wealth of information on the reactions of redox-active sites in proteins can be obtained by voltammetric studies in which the protein sample is arranged as a layer on an electrode surface. By carrying out cyclic voltammetry over a wide range of scan rates and exploiting the ability to poise or pulse the electrode potential between cycles, data are obtained that are conveniently (albeit simplistically) analysed in terms of plots of peak potentials against scan rate. A simple reversible electron-transfer process gives rise to a 'trumpet'-shaped plot because the oxidation and reduction peaks separate increasingly at high scan rate; the electrochemical kinetics are then determined by fitting to Butler-Volmer or Marcus models. Much more interesting though are the ways in which this 'trumpet plot' is altered, often dramatically, when electron transfer is coupled to biologically important processes such as proton transfer, ligand exchange, or a change in conformation. It is then possible to derive particularly detailed information on the kinetics, energetics and mechanism of reactions that may not revealed clearly or even at all by other methods. In order to interpret the voltammetry of coupled systems, it is important to be able to define 'ideal behaviour' for systems that are expected to show simple and uncoupled electron transfer. Accordingly, this paper describes results we have obtained for several proteins that are expected to show such behaviour, and compares these results with theoretical predictions.     

Instantaneous, stoichiometric generation of powerfully reducing states of protein active sites using Eu(II) and polyaminocarboxylate ligands

Addition of an equivalent of a polyaminocarboxylate ligand (L) to a solution of a redox protein and the aqua Eu2+ ion results in the instantaneous in situ generation of a very powerful reductant Eu(II)-L that can rapidly drive an electron stoichiometrically onto a redox centre having an extremely negative reduction potential (lower than -1 V): this is exemplified by straightforward generation of the super-reduced state of the Fe-protein of nitrogenase.     

Development of dinitrophenylated cyclodextrin derivatives for enhanced enantiomeric separations by high-performance liquid chromatography

The synthesis and evaluation of new dinitrophenyl (DNP) substituted beta-cyclodextrin (beta-CD) chiral stationary phases (CSPs) for the enantioseparation of various classes of chiral analytes by HPLC are presented. The dinitrophenyl substituted beta-CD derivatives are synthesized and covalently bonded to functionalized 5 microm spherical porous silica gel. These are the first reported derivatized cyclodextrin which contains pi-electron deficient substituents (i.e., pi-acidic moieties). The column performance in terms of their ability to separate enantiomers is evaluated. A variety of different dinitro-substituted aryl groups are investigated and compared. The pH of the mobile phase buffers, the buffer composition, the number and position of the dinitro groups on the phenyl ring substituent, the degree of substitution, and the bonding strategy all greatly affect the performance of the CSPs. A large variety of racemic compounds have been separated successfully on these CSPs. The bonded dinitrophenyl-derivatized cyclodextrins are stable in all three mobile phase modes, namely, the reversed-phase, polar organic, and normal phase modes. No degradation in column performance was observed in any mode of operation even after more than 1000 injections. The analytical applicability of these types of CSPs for enantiomeric separations is discussed in detail.     

Synthesis,Characterisation and Reactivity of Copper(I) Amide Complexes and Studies on Their Role in the Modified Ullmann Amination Reaction

A series of copper(I) alkylamide complexes have been synthesised; copper(I) dicyclohexylamide ( 1 ), copper(I) 2,2,6,6‐tetramethylpiperidide ( 2 ), copper(I) pyrrolidide ( 3 ), copper(I) piperidide ( 4 ), and copper(I) benzylamide ( 5 ). Their solid‐state structures and structures in [D₆]benzene solution are characterised, with the aggregation state in solution determined by a combination of DOSY NMR spectroscopy and DFT calculations. Complexes 1 , 2 and 4 are shown to exist as tetramers in the solid state by X‐ray crystallography. In [D₆]benzene solution, complexes 1 , 2 and 5 were found by using ¹H DOSY NMR to exist in rapid equilibrium between aggregates with average aggregation numbers of 2.5, 2.4 and 3.3, respectively, at 0.05 M concentration. Conversely, distinct trimeric, tetrameric and pentameric forms of 3 and 4 were distinguishable by one‐dimensional ¹H and ¹H DOSY NMR spectroscopy. Complexes 3 – 5 are found to react stoichiometrically with iodobenzene, in the presence or absence of 1,10‐phenanthroline as an ancillary ligand, to give arylamine products indicative of their role as potential intermediates in the modified Ullmann reaction. The role of phenanthroline has also been explored both in the stoichiometric reaction and in the catalytic Ullmann protocol.     

A Gas Chromatography-Molecular Rotational Resonance Spectroscopy Based System of Singular Specificity

We designed and demonstrated the unique abilities of the first gas chromatography–molecular rotational resonance spectrometer (GC-MRR). While broadly and routinely applicable, its capabilities can exceed those of high-resolution MS and NMR spectroscopy in terms of selectivity, resolution, and compound identification. A series of 24 isotopologues and isotopomers of five organic compounds are separated, identified, and quantified in a single run. Natural isotopic abundances of mixtures of compounds containing chlorine, bromine, and sulfur heteroatoms are easily determined. MRR detection provides the added high specificity for these selective gas-phase separations. GC-MRR is shown to be ideal for compound-specific isotope analysis (CSIA). Different bacterial cultures and groundwater were shown to have contrasting isotopic selectivities for common organic compounds. The ease of such GC-MRR measurements may initiate a new era in biosynthetic/degradation and geochemical isotopic compound studies.     

Enantioselective epoxidation of alkenes catalyzed by 2-fluoro-N-carbethoxytropinone and related tropinone derivatives

Several alpha-substituted N-carbethoxytropinones have been evaluated as catalysts for asymmetric epoxidation of alkenes with Oxone, via a dioxirane intermediate. alpha-Fluoro-N-carbethoxytropinone (2) has been studied in detail and is an efficient catalyst which does not suffer from Baeyer-Villiger decomposition and can be used in relatively low loadings. This ketone was prepared in enantiomerically pure form using chiral base desymmetrization of N-carbethoxytropinone. Asymmetric epoxidation catalyzed by 2 affords epoxides with up to 83% ee. Among other derivatives tested, the alpha-acetoxy derivative 7 affords the highest enantioselectivities.