Electron spin resonance study of copper(II) doped ferroelectric ammonium sulphate

Single crystal electron spin resonance studies of Cu2+ doped ferroelectric ammonium sulphate ((NH4)2SO4, Tc = 223 K) are reported at 300 and 77 K. The Cu2+ ion is found to enter the lattice interstitially with a trigonal bipyramidal coordination. Proton superhyperfine interaction is found for magnetic field directions close to the a-axis. Changes are observed in the 77 K recordings indicating a distortion of the trigonal bipyramid consistent with crystal structure data. An increase of the proton superhyperfine constant in the ferroelectric phase is indicative of stronger hydrogen bonding. The Cu2+ ion doped as an impurity in a trigonal bipyramid environment in a diamagnetic host lattice is reported for the first time.

Wrought aluminum-nickel alloys for high strength-high conductivity applications

Aluminum-Nickel alloys ranging from 0.06 pct to 6.1 pct (by wt) Ni have been developed for high strength-high conductivity applications. These alloys were produced by solidification in a permanent mold followed by homogenization, hot extrusion or hot rolling and cold drawing to wire form. This sequence of fabrication a) led to the production of fine fibrous dispersoids of NiAl3 as part of the Al-NiAl3 eutectic during the initial casting operation, b) permitted the retention of fine fibrous dispersiods of NiAl3 produced during casting without any significant coarsening during processing and c) led to uniform dispersion and general alignment of these fibrous dispersoids along a given direction in the product without any measurable fiber-matrix separation, extensive fiber-fragmentation or crack production in the matrix. These alloys can be processed to wire form as easily as aluminum and when processed by the above sequence, possess very attractive combination of high strength-high electrical conductivity. Tensile strengths range from 173 N/mm2 (at 0.6 pct Ni) to 241 N/mm2 (at 6.1 pct Ni) in combination with corresponding conductivity values between 62 pct IACS and 55.5 pct IACS. The wires also possess attractive yield strength; for instance, the 0.2 pct off-set strength of Al-6.1 pct Ni wire is 213 N/mm2. Using simple composite rules, the estimated strength and the conductivity of NiAl3 fibers were found to be 1380 N/mm2 and 18 pct IACS respectively, in these wires.

Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 mu m

A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mu m up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5)(Sigma(+)(u) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

X-ray studies of crystalline complexes involving amino acids. II. The crystal structure of L-arginine L-glutamate

Abstract is not available.

Interaction of palladium (II) with DNA

The nature of interaction of palladium(II) with calf thymus DNA was studied using viscometry, ultraviolet, visible and infrared spectrophotometry and optical rotatory disperison and circular dichroism measurements. The results indicate that Pd(II) interacts with both the phosphate and bases of DNA. The ORD/CD data indicate that the binding of Pd(II) to DNA brings about considerable conformational changes in DNA.

Preparation of Palladium(II) Complexes of Isonitrosoacetylacetoneimines Having O- and N-Coordinated Isonitroso Groups

Methods for the preparation of palladium(II) complexes of the type Pd(R-IAI)(IAI'), where IAI' is the anion of isonitrosoacetylacetoneimine and R-IAI, its N-alkyl or N-aryl derivative, are given.

Metal chelates in vinyl polymerization. II. Mechanism of initiation by Fe(DPM)3

The nature of the interaction between the unsaturated monomer and the chelate, Fe(DPM)3, is studied in detail. The interaction is found to occur only in solution. The stoichiometry of interaction and the equilibrium constant are evaluated. With the help of spectral evidence, attempts are made to point out the specific sites of interaction.

New ternary copper(II) complexes of L-alanine and heterocyclic bases: DNA binding and oxidative DNA cleavage activity

Four new ternary copper(II) complexes of alpha-amino acid having polypyridyl bases of general formulation [Cu(L-ala)(B)(H2O)](X)(1-4), where L-ala is L-alanine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2) and 5,6-phenanthroline dione (dione, 3), dipyrido[3,2:2',3'-f] quinoxaline (dpq, 4), and X = ClO4-/NO3- are synthesized, characterized by various spectroscopic and X-ray crystallographic methods. The complexes show a distorted square-pyramidal (4 + 1) CuN3O2 coordination geometry. The one-electron paramagnetic complexes (1-4) display a low energy d-d band near 600 nm in aqueous medium and show a quasi-reversible cyclic voltammetric response due to one-electron Cu(II)/Cu(I) reduction near - 100 mV (versus SCE) in DMF-0.1 M TBAP. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. All the complexes barring the complexes 1 and 3 are avid binder to the CT-DNA in the DNA minor groove giving an order: 4 > 2 >>>1, 3. The complexes 2 and 4 show appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA) as a reducing agent. Hydroxyl radical was investigated to be the DNA cleavage active species. Control experiments in the presence of distamycin-A show primarily minor groove-binding propensity for the complexes 2 and 4 to the DNA.

Responses of Scots pine to nickel and copper exposure and herbivory

The goal of this thesis was to examine the ecophysiological responses of Scots pine (Pinus sylvestris L.), with an emphasis on the oxidative enzyme peroxidase and plant phenolics to environmental stresses like elevated levels of nickel (Ni) and copper (Cu), and herbivory. The effects of Ni and Cu were studied in a gradient survey at a sulphur dioxide contaminated site in the Kola Peninsula, and with experiments in which seedlings were exposed to Ni mist or to Ni and Cu amended into the soil. In addition, experimental Ni exposure was combined with disturbance of the natural lichen cover of the forest ground layer. Pine sawfly attack was simulated in the early season defoliation experiment, in which mature Scots pine were defoliated (100 %) during two successive years in a dry, nutrient-poor Scots pine stand. In addition, the effect of previous defoliation on the growth of sawfly (Diprion pini L.) larvae was studied. Apoplastic peroxidase activity was elevated in the needles of pine in a Ni- , Cu- and SO2- polluted environment, which indicated an increased oxidative stress. Increased foliar peroxidase activity due to Ni contamination was shown in the experiment, in which Ni was added as mist. No such response was found in peroxidase acitivity of the roots exposed to elevated Ni and/or Cu in the soil. Elevated Ni in the soil increased the concentration of foliar condensed tannins, which are able to bind heavy metals in the cells. Addition of low levels of Ni in the soil appeared to benefit pine seedlings, which was seen as promoted shoot growth and better condition of the roots. Wet Ni deposition of 2000 mg m-2 reduced growth and survival of pine seedlings, whereas deposition levels 200 mg m-2 or 20 mg m-2 caused no effects in a 2-y lasting experiment. The lichen mat on the forest floor did not act as an effective buffer against the adverse impacts of heavy metals on pine seedlings. However, some evidence was found indicating that soil microbes profited from the lichen mat. Artificial defoliation increased peroxidase activity in the Scots pine needles. In addition, defoliation decreased nitrogen, diamine putrescine and glucose concentrations in the needles and increased the concentrations of several phenolic compounds, starch and sucrose. Previous artificial defoliation led to poor growth of sawfly larvae reared on the pines, suggesting delayed induced resistance in Scots pine. However, there was no consistent relationship between inducibility (proportional increase in a compound following defoliation) and adverse effects on the growth of pine sawfly larvae. The observed inducible responses in needle phenolics due to previous defoliation thus appear to represent non-specific responses against sawflies.

X-ray crystal structure of a ternary copper(II) vitamin B6 complex, hydroxo(2,2'-bipyridyl)(pyridoxinato) copper(II) monohydrate. A rare example of monodentate coordination of copper(II) by the hydroxyl ion

A ternary metal complex involving Vitamin B6 with the formula [Cu(bipy)(pn) (OH)]H2O (bipy = 2,2'²-bipyridine, PN = anionic pyridoxine) has been synthesized and studied in the solid state by means of spectroscopy and X-ray crystallography. The geometry around copper(II) is distorted square pyramidal, two oxygens from phenolic and 4-(hydroxymethyl) groups of pn, two nitrogens from bipy and an axial OH- ion forming the coordination sphere. In this structure pn exists in a new anionic form with deprotonation of the phenolic group. The structure also provides a rare example of monodentate hydroxyl coordination to copper.

A novel amino acid racemization in vitamin b6-amino acid schiff base copper complexes: crystal structures of aquo (5'-phosphopyridoxylidene-dl-tyrosinato) copper(II) 3.5H2O and aquo (5'-phosphopyridoxylidene-dl-phenylalaninato) copper(II) 2.5H2O

A novel racemization observed in the Vitamin B6-amino acid Schiff base complexes, aquo (5'-phosphopyridoxylidene-l-tyrosinato) copper(II) and aquo (5'-phosphopyridoxylidene-l-phenylalaninato) copper(II) is described. The racemization taking place in solution under mild acidic conditions (pH 5-6) was confirmed by CD studies and the products were characterized by single crystal X-ray diffraction. The structures of both complexes show almost parallel orientation of the aromatic side chain and the pyridoxal II-system. The activation of the αCsingle bondH group due to the intermolecular II- interaction is probably the reason for the unusual racemization observed.

Conformational studies of the triphenylphosphazenyl side chain in cyclophosphazenes. II. Crystal and molecular structure of 2,4,4,6,6,8,8-heptachloro-2-triphenylphosphazenylcyclotetra(phosphazene), N4P4Cl7(NPPh3)

Abstract is not available.