Voltammetric determination of iron(II) and iron(III) in standard rocks and other materials

Voltammetry at a rotating platinum electrode in concentrated electrolyte solutions containing HCl and LiCl is described for simultaneous determinations of iron(II) and iron(III) in a variety of materials. Applications of the method to some U.S. Geological Survey standard rocks, a Georgian clay, and an iron-containing multiple vitamin tablet are described. For materials which can be dissolved without altering the original iron(II)/ iron(III) ratio, this method enables the two valence states to be determined rapidly and simultaneously. The technique is precise (r.s.d. ≈ 2%) and relatively free from interference, and requires only a recording d.c. polarograph.     

Polarity and Conformatios of Phosphorylethylenes and Phosphorylacetates in Solution

Abstract

A series of derivatives R¹R²P(X)R³, where R¹=R²=Ph. R³= -CH=CH-Me, X=O(I); R¹=Me, R²=Ph, R³= -CH=CH₂, X=O(II); R¹=R²=Ph, R³= -CH=CH₂, X=Se(III) and R¹R²P(O)-CH₂C(O)OX, where R¹=Ph, R²= -CH=CH₂, X=Ment?(IV); R¹=Ph-2-OMe, R²=Ph, X=Ment?(V); R¹=R²=CH₂Ph, X=Et(I), were investigated by means of dipole moments method. The problem of conjugation in phosphorylethylenes and conformation behaviour of phosphorylacetates was considered. DM (exp.) of (I-IV), determined in CC1₄ solution are 4.48(I), 4.27(II), 4.97(III), 4.21(IV), 5.21(V) and 4.02 D (VI). The intramolecular electronic interactions of phosphoryl group with unsaturated fragment did not displays in polarity properties of compounds (I-III). The experimental dipole moments of derivatives (I-III) are equal to the calculated values of DM. DM (IV-VI) is very sensitive to orientation of the P=O and C=O polar bonds. Because DM (exp.) of these compounds very sensitive to its orientation. DM (calc.) for cis- and trans- orientation of P=O and C=O dipoles are really different, that allows to drow the conclution that, in the contrast to the crystal state, the corresponded dipoles prefer an anti array in solution.     

Hydrolysis and amine-capping in a glycol solvent as a route to soluble maghemite gamma-Fe2O3 nanoparticles

The preparation of capped metal oxide nanoparticles through the hydrolysis of metal salts is made arduous by the difficulty of dissolving long organic chain capping agents in water; by performing the reaction in propylene glycol under reflux, instead of water, we are able to hydrolyse FeCl3 in the presence of n-octylamine to obtain (repeatedly) soluble, monodisperse approximately 5 nm gamma-Fe2O3 particles that display a tendency to aggregate into superlattices.     

A general preparation of (Z)-1-fluorostilbene derivatives for the design of conformationally restricted peptidomimetics

The preparation of (Z)-1-fluoro-2-bromostyrenes provides a general route for the formation of (Z)-1-fluorostilbene derivatives as configurationally stable spacial linkers for the design of conformationally restricted peptidomimetics. Palladium-catalyzed aryl Suzuki and Stille cross-coupling reactions have been surveyed to proceed with complete retention of fluoroalkene geometry, and permit the direct incorporation of a variety of aryl and heteroaromatic substituents.     

Petty's projection inequality and Santalo's affine isoperimetric inequality

Using results of K. Kiener and the Riesz-Sobolev convolution inequality we give a new proof of Petty's projection inequality. By the same method we also obtain a proof of Santalo's affine isoperimetric inequality.Supported in part by BSF and Erwin Schrödinger Auslandsstipendium J0630, J0804.     

Topological analysis of complex molecular surfaces

An algorithm for the calculation of local and global curvatures of molecular surfaces is presented. The analysis is based on a surface representation as a set of points in 3-D space (“dotted surface” representation). The surface data are used to subdivide the surfac into domains with different curvatures. All domains are characterized by a reference point with a corresponding curvature profile specifiying the topological properties in its neighborhood. The curvature profiles provide a method for a systematic comparison of the shapes of different molecules. Such a strategy is important for the treatment of molecular recognition problems. The enzyme-inhibitor complex trypsin/BPTI was chosen to demonstrate the scopes of the method.     

The Franssen effect illusion in budgerigars (Melopsittacus undulatus) and zebra finches (Taeniopygia guttata)

The properties of the Franssen effect (FE) were measured in budgerigars and zebra finches. To elicit the FE, listeners are presented with a signal which has been split into a transient component, carrying an abrupt onset and ramped offset and separated in space from the sustained component which has a slowly rising onset and longer duration. When these two signals are played under certain conditions, the perception is that of a long-duration steady state tone being played at the location of the transient. The birds were trained using operant conditioning methods on a categorization task to peck a left key when presented with a stimulus from a left speaker and to peck a right key when presented with a stimulus from a right speaker. Once training was completed, FE stimuli were presented during a small proportion of trials. The FE was measured at speaker separations of 60 degrees and 180 degrees in both echoic and echoic-reduced conditions. Both species of birds exhibited the FE, although to varying degrees, across conditions. These results show that nonmammals also experience the FE illusion in confusing listening situations in a manner similar to mammals, suggestive of similar auditory processing mechanisms.     

Functionalized-graphene modified graphite electrode for the selective determination of dopamine in presence of uric acid and ascorbic acid

Graphene is chemically synthesized by solvothermal reduction of colloidal dispersions of graphite oxide. Graphite electrode is modified with functionalized-graphene for electrochemical applications. Electrochemical characterization of functionalized-graphene modified graphite electrode (FGGE) is carried out by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The behavior of FGGE towards ascorbic acid (AA), dopamine (DA) and uric acid (UA) has been investigated by CV, differential pulse voltammetry (DPV) and chronoamperommetry (CA). The FGGE showed excellent catalytic activity towards electrochemical oxidation of AA, DA and UA compared to that of the bare graphite electrode. The electrochemical oxidation signals of AA, DA and UA are well separated into three distinct peaks with peak potential separation of 193mv, 172mv and 264mV between AA-DA, DA-UA and AA-UA respectively in CV studies and the corresponding peak potential separations in DPV mode are 204mv, 141mv and 345mv. The FGGE is successfully used for the simultaneous detection of AA, DA and UA in their ternary mixture and DA in serum and pharmaceutical samples. The excellent electrocatalytic behavior of FGGE may lead to new applications in electrochemical analysis.     

Near 100% selectivity in anion exchange reactions of layered zinc hydroxy nitrate

The anionic clay, zinc hydroxy nitrate was found to selectively intercalate fluoride ions from a mixture of halide ions and chloride ions from a mixture of chloride, bromide and iodide ions. In a binary mixture of chloride and bromide ions, the selectivity for chloride ions was very high (94%) even when the bromide concentration was eight times in excess. The selectivity was achieved in both concentrated and dilute salt solutions. The trend in selectivity observed here is different from what has been observed for layered double hydroxides.