The complexes of aluminium,gallium, and indium with calmagite: Evaluation of stepwise stability constants

Summary Calmagite [1-(1-hydroxy-4-methyl-2-phenyl azo)-2-naphthol sulphonic acid], dissociates in two steps. It forms violet complexes with Al³⁺, Ga³⁺ and In³⁺. The stepwise proton-ligand stability constants of calmagite and stepwise metal-ligand stability constants of these complexes were evaluated by potentiometric titration technique ofBjerrum andIrving andRossotti. The order of the stabilities of complexes is In³⁺ > Ga³⁺ > > Al³⁺.

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Zusammenfassung Camalgit [1-(1-Hydroxy-4-methyl-2-phenylazo)-2-naphtholsulfonsäure] dissoziiert in zwei Stufen und bildet violette Komplexe mit Al(III), Ga(III) und In(III). Die Konstanten der Dissoziationsstufen der freien Säure und die der Metallkomplexe wurden potentiometrisch nachBjerrum bzw.Irving undRossotti ermittelt. Die Stabilität der Komplexe nimmt in der Reihe In(III) > Ga(III) > Al(III) ab.

     

Some chemistry of mixed ligand complexes of platinum

Simple synthetic routes to the mixed ligand complexes PtLL'X₂ and PtLL'XY (L' = PEt₃; L = phosphine, arsine, etc.; X = Cl and Y = Cl, H or Me) are described; unexpectedly, these display an extensive chemistry without disproportionation, although in some cases ligand scrambling does occur.     

Itinerant electron ferromagnetism in Sr2+-, Ca2+-, and Ba2+-doped rare-earth orthocobaltites (Ln3+1−xM2+xCoO3)

Electronic and magnetic properties of Ln_1?xSr_xCoO₃ (Ln = Pr, Nd, Sm, Eu, and Gd) systems show that above a critical value of x, the d electrons become itinerant while the materials become ferromagnetic at low temperatures. The ferromagnetic component increases with increase in x and decrease in temperature. The Curie temperature increases with x and decreases with decrease in the size of the rare-earth ion. Incorporation of Ba²⁺ in LaCoO₃ favors itinerant electron ferromagnetism relative to Sr²⁺ while Ca²⁺ is less favorable than Sr²⁺.     

Effects of chain length and heat treatment on the nanotribology of alkylsilane monolayers self-assembled on a rough aluminum surface

The conformational order of alkylsilane monolayers self-assembled on a rough aluminum surface is affected by the molecular chain length and the thermal history of the sample. These monolayers have been characterized by grazing angle FTIR spectroscopy. Tribological mechanisms were explored using initial molecular conformation order, sliding distance, normal load, and substrate compliance as experimental variables. Results indicate that the initial conformational disorder of the molecules determines the level of friction at the commencement of sliding. Adverse changes in dynamic friction and monolayer life during sliding are not thermally induced but are related to substrate roughness and local plasticity. Plastic deformation reduces the spatial density of the alkylsilane monolayer and is accentuated by an increase in the normal load.     

Structure-activity study of antiepilepticN-aryl-isoxazolecarboxamides/N-isoxazolylbenzamide analogs using Wiener's topological index

The relationship between Wiener's topological index and the antiepileptic activity of a series ofN-aryl-isoxazole carboxamides/N-isoxazolylbenzamide analogs has been investigated. Values of Wiener's topological index for 69 compounds constituting the training set were computed and an active range was identified. Each analog was subsequently assigned an activity which was then compared with the reported antiepileptic activity against the maximal electroshock seizure (MES) test. Due to significant correlation between antiepileptic activity and Wiener's topological index, it was possible to predict antiepileptic activity with an accuracy of 91 % in the active range.     

Expected and unexpected results from combined beta-hairpin design elements

A model beta-hairpin dodecapeptide [EFGWVpGKWTIK] was designed by including a favorable D-ProGly Type II' beta-turn sequence and a Trp-zip interaction, while also incorporating a beta-strand unfavorable glycine residue in the N-terminal strand. This peptide is highly folded and monomeric in aqueous solution as determined by combined analysis with circular dichroism and 1H NMR spectroscopy. A peptide representing the folded conformation of the model beta-hairpin [cyclic(EFGWVpGKWTIKpG)] and a linear peptide representing the unfolded conformation [EFGWVPGKWTIK] yield unexpected relative deviations between the CD and 1H NMR spectroscopic results that are attributed to variations in the packing interactions of the aromatic side chains. Mutational analysis of the model beta-hairpin indicates that the Trp-zip interaction favors folding and stability relative to an alternate hydrophobic cluster between Trp and Tyr residues [EFGYVpGKWTIK]. The significance of select diagonal interactions in the model beta-hairpin was tested by rearranging the cross-strand hydrophobic interactions to provide a folded peptide [EWFGIpGKTYWK] displaying evidence of an unusual backbone conformation at the hydrophobic cluster. This unusual conformation does not appear to be a result of the glycine residue in the beta-strand, as replacement with a serine results in a peptide [EWFSIpGKTYWK] with a similar and seemingly characteristic CD spectrum. However, an alternate arrangement of hydrophobic residues with a Trp-zip interaction in a similar position to the parent beta-hairpin [EGFWVpGKWITK] results in a folded beta-hairpin conformation. The differences between side chain packing of these peptides precludes meaningful thermodynamic analysis and illustrates the caution necessary when interpreting beta-hairpin folding thermodynamics that are driven, at least in part, by aromatic cross strand interactions.     

Electron transfer in the reduction of primary halides by metal hydrides

The reactions of various main-group metal hydrides with 1-halo-5-hexenes and with 1-halo-2,2-dlmethyl-5-hexenes produce both straight chain and cyclized reduction products. The formation of cyclic hydrocarbons clearly indicates the presence of radical intermediates during the course of these reactions.     

Bromine cyanide as titrimetric oxidant in non-aqueous media

Bromine cyanide has been used for the potentiometric determination of sulphide, sulphite, thiocyanate, iodide, tin(II), arsenic(III),hydrazine hydrate, phenylhydrazine, 1,1-methylphenyldrazine and chloralhydrazine in glacial acetic acid and 1 : 1 acetic acid-acetic anhydride mixture, of thiourea, ethylthiourea, isopropylthiourea, benzylthiourea, alpha-phenylthiourea and o-tolythiourea in methanol, and of sodium methyl-, ethyl-,dimethyl-, diehtyl- and isopropyldithiocarbamates in ehtanol and acetonitrile media. The behaviour of bromine cyanide in these non- aqueous solvents has been compared with its behaviour in aqueous medium and with that of iodine cyanide in these non-aqueous solvents.     

Critical Phenomena in the Clouding Behavior of Nonionic Surfactants Induced by Additives

Effects of anionic surfactants, hydrotropes, and electrolytes on the cloud point of Triton X-100 have been studied over six decades of additives concentrations. A comprehensive look at all the data reveals significant new learnings. While anionic surfactants and hydrotropes affect the cloud point of non-ionics at ultra low (monomeric) concentrations, electrolytes exhibit a minimum critical concentration above which they cast their effect. This suggests that the former work by modifying the surface charge of non-ionic micelles (i.e., by affecting the solute), whereas the latter work by modifying the properties of the bulk medium. Above their respective critical concentrations, salting-out electrolytes decrease the cloud point while salting-in electrolytes increase it, the trends being linear with additive concentration in either case. The magnitude of the effect of anionic surfactants and hydrotropes increases gradually with increasing concentration till their respective cmc's are reached and then there is a sharp rise in the cloud point. Copyright 1999 Academic Press.     

Synthesis,structural and biochemical aspects of titanocene and zirconocene chelates of acetylferrocenyl thiosemicarbazones

The reactions of bis(cyclopentadienyl)titanium(IV)/zirconium(IV) dichloride with a new class of organometallic thiosemicarbazones (LH), derived by condensing acetylferrocene with substituted thiosemicarbazides, have been studied and two types of bimetallic products, viz. [Cp₂M(L)Cl] (M = Ti or Zr) and [CpZr(L)₃], have been isolated. On the basis of various physicochemical and spectral studies, five- and seven-coordinate structures have been assigned to these derivatives, respectively. Attempts have been made to establish a correlation between biological activity and the structures of the products.