Exchange interactions in bis(diethyldithiocarbamato)copper(II), Cu(detc)2

The exchange coupling constant J in bis(diethyldithiocarbamato)copper(II) has been derived through analysis of the EPR g values and linewidth as a function of orientation, frequency and temperature. The single line in the ac* plane is due to the averaging of the fine-structure splitting by interdimer exchange for which a lower limit of 0.02 cm^?1 has been obtained. Analysis of the spectra in the bc plane gives an estimate of 0.008 cm^?1 for the intersite exchange.     

A reinvestigation of the reaction between titanium(iv) and salicylic acid in concentrated sulphuric acid

It is shown that the coloured species formed between TiO(2+) and salicylic acid in concentrated sulphuric acid may be a pi-complex rather than a chelate. Similar species are formed by other hydroxybenzoic acids where chelating sites for TiO(2+) are not available. The ultraviolet and NMR spectral characteristics of hydroxybenzoic acids in water, concentrated sulphuric acid and deuterochloroform are presented as evidence for the pi-complex formation. The reaction of VO(2+) with salicylic acid in concentrated sulphuric acid is shown to be due to increasing electron-donation in the pi-component of the V-O bond of VO(H(2)O)(5)(2+) as the concentration of sulphuric acid is increased, and not to the presence of salicylic acid.     

Radiation-induced copolymerization of hydrophilic monomers with vinyl acetate: Synthesis and thermal properties

Radiation-induced copolymerization of hydrophili+ monomers, viz., 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), and N-vinyl-2-pyrrolidone (NVP) with vinyl acetate (VAc) was carried out in bulk at 25°C. The copolymer composition was determined from the acetoxy content. The copolymerization parameters were determined by a graphical method and compared with those determined by the Yezrielev, Brokhina, and Roskin (YBR) method. Thermal properties of copolymers were studied by GC-MS. Probable mechanisms were suggested from the products obtained.     

Synthesis of binaphthols over mesoporous molecular sieves

Mesoporous aluminosilicates (Al-containing NaMCM-41) were applied as catalyst supports for oxidative coupling of β-naphthol and substituted β-naphthols due to their remarkable features such as surface area, ordered mesopores and high thermal stability. The NaMCM-41 supported copper catalysts prepared by impregnation method, and Cu-NaMCM-41 was prepared by incorporating copper during synthesis. Oxidative coupling of β-naphthol reaction was studied using molecular oxygen as oxidant. The copper supported NaMCM-41 catalysts were prepared with different Si/Al ratios and calcined from 120 to 420 °C were observed to show varied product selectivity. The NaMCM-41 supported copper catalysts and Cu-NaMCM-41 were more active than the corresponding Cu/Fe supported on NaY zeolite. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), UV–DRS, ICPMS and BET surface area techniques and the reaction products were confirmed by ¹H-NMR, FTIR and HRMS. An attempt has been made to explain the product selectivity of the catalysts discussed with the above techniques. The high dispersion of Cu⁺² species observed in the catalysts having high Si/Al ratios in NaMCM-41 support and catalysts that are calcined at low temperatures, i.e. less than 420 °C, yielded an unexpected product perylene diol. A comparatively low dispersion of Cu⁺² species, noticed in catalysts having low Si/Al ratios and calcined at high temperatures, yielded binapthol as the coupled product. The effect of the variation of catalyst and the solvent are also studied.     

Kinetics of dissociation of tris-1,10-phenanthroline-iron(II) complex cation in aqueous acetic acid solutions

The reaction under study is first order in the complex ion over the entire composition range of the mixed solvent. A minimum amount of mineral acid is needed for completion of the reaction (formation of colorless products), but the rate is practically acid-independent. The influence of solvent composition and some common ions on the reaction rate have been examined. A reaction mechanism consistent with the rate behavior is proposed where water is shown as an active participant in the dissociation process. A plausible explanation for the retardation effect of HSO₄ ⁻ as against the accelerating effect of Cl⁻ under water-scarce conditions is provided.     

Solvent extraction of Tm(III) by sulfoxides and mixtures of DPSO (di-N-pentyl sulfoxide) and HTTA (thenoyl-trifluoroacetone) from perchlorate and thiocyanate media

Extraction of Tm(III), from thiocyanate media, by different sulfoxides (R₂SO) has revealed that the extractable complex is Tm(SCN)₃·4 R₂SO. When mixtures of DPSO and HTTA are used for the extraction of Tm(III) from thiocyanate or perchlorate media, synergistic enhancement of the extraction of Tm(III) results. The complexes responsible for the enhanced extraction are Tm(TTA)₃·DPSO and Tm(TTA)₃·2 DPSO when perchlorate media were employed for the extraction and Tm(SCN)(TTA)₂·2 DPSO and Tm(SCN)₂(TTA)·3 DPSO, in addition to the above two when a thiocyanate medium was employed for the extraction. Values of equilibrium constants for some equilibria encountered in the extraction of Am(III) and Tm(III) by mixtures of DPSO and HTTA are given.     

A chemical enhancement method for the spectrophotometric determination of trace amounts of arsenic

A highly sensitive spectrophotometric method for the determination of 0.03-1.0 microg of arsenic is described. After extraction as AsI(3) into benzene, it is selectively stripped into water. Both the arsenic(III) and iodide present in the aqueous phase are made to react with iodate in acidic medium in the presence of chloride to form the anionic chloro complex, ICl(-)(2). The determination is completed after extraction of ICl(-)(2) species as an ion-pair with Rhodamine 6G into benzene and measuring the absorption of the extract at 535 nm. The coefficient of variation is 1.5% for 10 determinations of 0.5 microg of arsenic. The method has been applied to the determination of arsenic content in plant materials, high purity iron, copper base alloys and inorganic arsenic levels of natural waters.     

Coherence spectroscopy in dissipative media: a Liouville space pathway approach

We address the possibility of using coherent control tools to extract useful information about the interaction of a system with a dissipative environment. To that end we extend previous work, which developed a coherence spectroscopy based on two-pathway excitation phase control, from the isolated molecule limit to dense media. Specifically, we explore the properties of the channel phase, an observable of energy-domain two-pathway excitation experiments that was shown in the isolated molecule limit to carry information about the phase properties of the material system. Our analysis is based on the combination of steady state and time-dependent analytical perturbative approaches within the density matrix formalism, complemented by nonperturbative numerical simulations. We find that the channel phase carries significantly richer information in the presence of decoherence mechanisms than in their absence. In particular, rescattering events in the structured continuum introduce new features in the channel phase spectrum, whose structure conveys information about both the molecular continuum and the system bath interaction.     

DNA binding and oxidative cleavage activity of ternary (l-proline)copper(II) complexes of heterocyclic bases

Ternary copper(II) complexes [Cu(l-pro)(B)(H₂O)](NO₃) (1, 2) where l-pro = l-proline, B is a N,N-donor heterocyclic base, viz. 2,2′-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), are synthesized, characterized, and their DNA binding and cleavage activity studied. The bpy complex (1) is structurally characterized by single-crystal X-ray crystallography. The complexes show the presence of a distorted square-pyramidal (4 + 1) CuN₃O₂ coordination geometry. Complex [Cu(l-pro)(bpy)(H₂O)](NO₃) (1) crystallizes in the triclinic space group P1 with unit cell parameters: a = 7.082(3) Å, b = 10.483(5) Å, c = 11.581(5) Å, α = 89.700(7)°, β = 83.488(8)°, γ = 84.109(8)° and V = 849.7(7) Å³. The one-electron paramagnetic complexes display a d–d band near 600 nm in water and show a cyclic voltammetric response due to Cu(II)/Cu(I) couple near 0.1 V (versus SCE) in Tris–HCl buffer–0.1 M KCl. Binding interactions of the complexes with calf thymus (CT) DNA have been investigated by emission, absorption, viscosity and DNA thermal denaturation studies. The phen complex displays significant binding propensity to the CT DNA giving an order: 2 (phen)  1 (bpy). The bpy complex does not show any apparent binding to the DNA and hence poor cleavage efficiency. Complex 2 shows efficient oxidative cleavage of SC-DNA in the presence of 3-mercaptopropionic acid (MPA) involving hydroxyl radical species as evidenced from the control data showing inhibition of DNA cleavage in the presence of DMSO and catalase.