Theoretical Treatment of Interaction Parameters in Multicomponent Metallic Solutions

A new theoretical equation for interaction parameter in multicomponent metallic solutions is developed using the pseudopotential formalism coupled with the free energy of the hard sphere system. The approximate expression for the pseudopotential term is given in terms of the heat of solution at infinite dilution, to allow easy evaluation of the interaction parameter in various multicomponent systems. This theory has been applied to 23 non-ferrous alloys based on Pb, Sn, Bi and indium. Comparison with the results of previous theoretical calculations using only the hard sphere model suggests that the inclusion of the pseudopotential term yields a quantitatively more correct prediction of interaction parameters in multicomponent metallic solutions. Numerical calculations were also made for 320 Fe-base solutions relevant to steelmaking and the agreement between calculation and experimental data appears reasonable, with 90% reliability in predicting the correct sign.

Thermodynamic consistency of the interaction parameter formalism

The apparent contradiction between the exact nature of the interaction parameter formalism as presented by Lupis and Elliott and the inconsistencies discussed recently by Pelton and Bale arise from the truncation of the Maclaurin series in the latter treatment. The truncation removes the exactness of the expression for the logarithm of the activity coefficient of a solute in a multi-component system. The integrals are therefore path dependent. Formulae for integration along paths of constant Xi,or X i/Xj are presented. The expression for In γsolvent given by Pelton and Bale is valid only in the limit that the mole fraction of solvent tends to one. The truncation also destroys the general relations between interaction parameters derived by Lupis and Elliott. For each specific choice of parameters special relationships are obtained between interaction parameters.

Mechanism of interaction of O-amino-D-serine with sheep liver serine hydroxymethyltransferase

The mechanism of interaction of 0-amino-D-serine (OADS) with sheep liver serine hydroxymethyltransferase (EC 2.1.2.1) (SHMT) was established by measuring changes in the enzyme activity,absorption spectra, circular dichroism (CD) spectra, and stopped-flow spectrophotometry. OADS was a reversible noncompetitive inhibitor (Ki = 1.8 pM) when serine was the varied substrate. The first step in the interaction of OADS with the enzyme was the disruption of enzyme-Schiff base, characterized by the rapid disappearance of absorbance at 425 nm (6.5 X lo3 M-' s-') and CD intensity at 430 nm. Concomitantly,there was a rapid increase in absorbance and CD intensity at 390 nm. The spectral properties of this intermediate enabled its identification as pyridoxal 5'-phosphate (PLP). These changes were followed by a slow unimolecular step (2 X s-') leading to the formation of PLP-OADS oxime, which was confirmed by its absorbance and fluorescence spectra and retention time on high-performance liquid chromatography. The PLP-OADS oxime was displaced from the enzyme by the addition of PLP as evidenced by the restoration of complete enzyme activity as well as by the spectral properties. The unique feature of the mechanism proposed for the interaction of OADS with sheep liver SHMT was the formation of PLP as an intermediate.

Mechanism of interaction of the antileukemic drug cytosine arabinoside with aromatic peptides : role of sugar conformation and peptide backbone

Interaction of the antileukemic drugs, cytosine-arabinoside (Ara-C) and adenosine-arabinoside (Ara-A) and a structural analogue, cytidine, with aromatic dipeptides has been studied by fluorescence and NMR spectroscopy. Ara-C and cytidine bind tryptophanyl and histidyl dipeptides but not tyrosyl dipeptides, while Ara-A does not bind to any of them. Both studies indicate association involving stacking of aromatic moieties. NMR spectra also indicate a protonation of the histidine moiety by Ara-C. In case of cytidine, the chemical shifts observed on binding to His-Phe imply that the backbone protons of the dipeptide participate in the binding. The conformation of the sugar and the base seem to play a very important role in the binding phenomenon as three similar molecules, Ara-C, Ara-A and cytidine bind in totally different ways.

Interaction of metal ions with nucleic acids and related compounds. II. Studies on Au(III)-nucleic acid system

The nature of interaction of Au(III) with nucleic acids was studied by using methods such as uv and ir spectrophotometry, viscometry, pH titrations, and melting-temperature measurements. Au(III) is found to interact slowly with nucleic acids over a period of several hours. The uv spectra of native calf-thymus DNA 9pH 5.6 acetate buffer containing (0.01M NaCIO4) showed a shift in λ max to high wavelengths and an increase in optical density at 260 nm. There was a fourfold decrease in viscosity (expressed as ηsp/c). The reaction was faster at pH 4.0 and also with denatured DNA (pH 5.6) and whole yeast RNA (pH 5.6). The order of preference of Au(III) (as deduced from the time of completion of reaction) for the nucleic acids in RNA > denatured DNA > DNA. The reaction was found to be completely reversible with respect KCN. Infrared spectra of DNA-Au(III) complexes showed binding to both the phosphate and bases of DNA. The same conclusions were also arrived at by melting-temperature studies of Au(III)-DNA system. pH titrations showed liberation of two hydroxylions at r = 0.12 [r = moles of HAuCl4 added per mole of DNA-(P)] and one hydrogen ion at r = 0.5. The probable binding sites could be N(1)/N(7) of adenine, N(7) and/or C(6)O of guanine, N(3) of cytosine and N(3) of thymine. DNAs differing in their (G = C)-contents [Clostridium perfingens DNA(G = C, 29%), salmon sperm DNA (G + C, 42%) and Micrococcus lysodeikticus DNA(G + C, 29%), salmon sperm DNA (G = C, 72%)] behaved differently toward Au(III). The hyperchromicity observed for DNAs differing in (G + C)-content and cyanide reversal titrations indicate selectivity toward ( A + T)-rich DNA at lw values of r. Chemical analysis and job's continuous variation studies indicated the existence of possible complexes above and below r = 1. The results indicate that Au(III) ions probably bind to hte phosphate group in the initial stages of the reaction, particularly at low values of r, and participation of the base interaction also increases. Cross-linking of the two strands by Au(III) may take place, but a complete collapse of the doulbe helix is not envisaged. It is probable that tilting of the bases or rotaiton of the bases around the glucosidic bond, resulting in a significant distrotion of the double helix, might take place due to binding of Au(III) to DNA.

Interaction of melittin with endotoxic lipid

Several amphipathic and cationic substances are known to bind lipid A, the toxic component of bacterial lipopolysaccharides. In this report, we have characterized, by fluorescence methods, the interaction of melittin, an amphipathic and basic 26-residue polypeptide isolated from bee venom, with lipid A. The stoichiometry of the complex appears to be two molecules of melittin to one of lipid A with a dissociation constant of 2.5 × 10 −6 M. The binding of melittin not only modifies the endotoxic properties of lipid A in a number of biological assays, but also results in abrogation of the hemolytic activity of melittin. A model of the complex is proposed based on the known structures of lipid A and melittin, and the observed stoichiometry of binding.

Anatase-rutile transformation in Fe/TiO2, Th/TiO2 and Cu/TiO2 catalysts and its possible role in metal-support interaction

Based on in-situ Mossbauer and X-ray diffraction studies, it is shown that in the Fe/TiO2 catalyst, the anatase-rutile transformation of the TiO2 support is facilitated by the Fe2+ ions formed during the reduction. The transformation occurs at lower temperatures in Th/TiO2 and Cu/TiO2 compared to pure TiO2. In general, the transformation of anatase to rutile seems to occur at or below the temperature (approximately 770 K) at which strong-metal-support-interaction manifests itself.

Therapeutic change in interaction

A process of change within a single case of cognitive-constructivist therapy is analyzed by means of conversation analysis (CA). The focus is on a process of change in the sequences of interaction, which consist of the therapist’s conclusion and the patient’s response to it. In the conclusions, the therapist investigates and challenges the patient’s tendency to transform her feelings of disappointment and anger into self-blame. Over the course of the therapy, the patient’s responses to these conclusions are recast: from the patient first rejecting the conclusion, to then being ambivalent, and finally to agreeing with the therapist. On the basis of this case study, we suggest that an analysis that focuses on sequences of talk that are interactionally similar offers a sensitive method to investigate the manifestation of therapeutic change. It is suggested that this line of research can complement assimilation analysis and other methods of analyzing changes in a client’s talk.

Frame Soil Interaction And Winkler Model

The Winkler spring model is the most convenient representation of soil support in the domain of linear elasticity for framed structure-soil interaction analyses. The closeness of the analytical results obtained using this model with those corresponding to the elastic half-space continuum has been investigated in the past for foundation beams. The findings, however, are not applicable to framed structures founded on beam or strip footings. Moreover, the past investigations employ the concept of characteristic length which does not adequately account for the stiffness contribution of the superstructure. A framed structure on beam foundation can be described parametrically by the ratios of stiffnesses of superstructure and foundation beams to that of soil. For a practical range of soil allowable pressures, the ranges of these relative stiffness ratios have been established. The present study examines the variation between interactive analyses based on Winkler springs with those using the half-space continuum over these ranges of relative stiffness ratios. The findings enable the analyst to undertake a Winkler spring-based-interaction analysis with knowledge of the likely variation of values with those derived for the more computation-intensive half-space continuum.