Synthesis, structure, and electronic and EPR spectra of copper(II) complexes containing the [CuBr4]2- anion and triphenylarsine oxide

The preparation and characterization of (Ph3AsOH)2[CuBr4] and [Cu(Ph3AsO)4][CuBr4] are reported (Ph3AsO = triphenylarsine oxide). Crystallographic analysis of the monoclinic crystals of (Ph3AsOH)2[CuBr4] (space group C2/c, a = 17.569 (3) Å, b = 13.090 (2) Å, c = 16.933 (2) Å, and β = 105.64 (2)°, R = 0.055 and Rw = 0.057) revealed the presence of compressed [CuBr4]2- tetrahedra of C2 symmetry with Cu-Br distances of 2.340 (1) and 2.437 (1) Å and trans-Br-Cu-Br angles of 139.2 (1) and 122.4 (1)°. The oxonium cations hydrogen bond to the bromine atoms involved in the longer Cu-Br bonds and the smaller trans-Br-Cu-Br angle. Single-crystal electronic and EPR spectra are interpreted in terms of the observed [CuBr4]2- geometry. Analysis of the electronic and EPR spectra of [Cu(Ph3AsO)4][CuBr4] led to the postulation of the presence of planar [Cu(Ph3AsO)4]2+ cations and distorted tetrahedral [CuBr4]2- anions. © 1992 American Chemical Society.

Influence of polymerization on the synthesis of SrTiO3: Part II. Particle and agglomerate morphologies

Morphologies of SrTiO3 particles and agglomerates synthesized by the traditional Pechini route and by the polymer precipitation route were characterized by the nitrogen adsorption/desorption technique and by transmission electron microscopy (TEM). A cluster structure of nanometric particles forming large agglomerates which are broken during pressing followed by cluster rearrangement was observed. The mean particle size is larger for SrTiO3 obtained by the Pechini route and is related to the precursor thermal decomposition and particle growth during calcination. The particle growth is controlled by neck growth among particles and further motion of the particle boundary. © 1995.

Energy of the Photosubstitutionally Reactive Excited State of Pentaammine(pyridine)ruthenium(II)

The photosensitized aquation of pentaammine(pyridine)ruthenium(II) by several dyes has been studied under conditions where only the sensitizers absorb light. The ratio of the quantum yields for ammine and pyridine substitution was the same as that for direct photoaquation. Sensitization was effective with singlet sensitizers Rhodamine-B (17 452 cm -1) and Safranine-T (17 690 cm -1), as well as the triplet sensitizer biacetyl (19 000 cm -1), but no reaction was observed with Neutral-Red (16 900 cm -1). The results indicate that the excited state precursor of the observed photosubstitution in the complex lies in the energy range between 17 000 and 17 700 cm -1.

Resonance and chaos: II. Exterior resonances and asymmetric libration

The motion of a test particle in the vicinity of exterior resonances is examined in the context of the planar, circular, restricted three-body problem. The existence of asymmetric periodic orbits associated with the 1 : n resonances (where n = 2, 3, 4, 5) is confirmed; there is also evidence of asymmetric resonances associated with larger values of n. A detailed examination of the evolution of the family of orbits associated with the 1:2 resonance shows the sequence that leads to asymmetric libration. On the basis of numerical studies of the phase space it is concluded that the existence of asymmetric libration means that the region exterior to the perturbing mass is more chaotic than the interior region. The apparent absence of 'particles' in 1 : n resonances in the solar system may reflect this inherent bias.

Preparation, characterization and electrochemical studies of dinuclear copper(II) complexes with pseudohalides and bidentate amines on platinum electrode in acetonitrile

The complexes: [Cu(N 3) 2(N,N-diEten)] 2, [Cu(N 3) 2(tmeen)] 2, [Cu(N 3)(NCO)(N,N-diEten)] 2, [Cu(N 3) 2(N,N′-diMeen)] 2 and [Cu(N 3)(NCO)(tmeen)] 2 were prepared, characterized and their electrochemical behavior was investigated by cyclic voltammetry and controlled potential electrolysis. Cyclic voltammograms for all complexes studied are similar and exhibit one pair of current peaks in the range of -0.65 to +0.0 V. The number of electrons obtained from controlled potential electrolysis at ca. -0.55 V for all compounds was 1.8 ≤ n ≤ 2.1, indicating that both copper(II) metallic centres in the molecule were reduced to copper (I). Comparing the peak potential values for these complexes one can observe that the redox process corresponding to copper(II)/copper(I) couple is slightly influenced by the σ-basicity of the ligands. © 1997 Soc. Bras. Química.

Pre-concentration of Cd(II), Cr(III), Cu(II) and Ni(II) on a column packed with free carboxymethylcellulose (CMCH)

Carboxymethylcellulose packed in to a glass column was used to pre-concentrate metallic cations from aqueous solutions. The pre-concentrated metal cations are directly eluted from the column using 5.0 mL of 1.0 mol L -1 hydrochloric acid. The optimum pre-concentration conditions are given (glass column, 16 cm length, 0.80 cm i.d., stationary phase height of 12 cm, flow-rate, 1.5 mL min -1). The recuperation efficiency achieved is greater than 95%, while the enrichment factor is 10 for 50 mL of solution (0.50 mg L -1 each).

Structure of cobalt (II) perchlorate adsorbed on silica gel surface chemically modified with benzimidazole molecule

Covalently attached benzimidazole molecules on silica gel surface, ≡SiL (where L = N-propyl-benzimidazole), adsorbs Co(ClO4)2 from non-aqueous solvent by forming a surface complex according to the reaction: m ≡SiL + Co(ClO4)2 → (≡SiL)mCo(ClO4)2. The equilibrium constant and the adsorption capacity, determined by applying the Langmuir equation were b = 3.0 × 103 L mol-1 and Ns= 0.098 × 10-3 mol g-1, respectively. The metal is bonded through the nitrogen atom and the perchlorate ion is not coordinated. The ESR study indicated that the complex has essentially an octahedral geometry with tetragonal distortion, with the electrons of the four nitrogen atoms interacting with the cobalt central metal ion in the equatorial plane. Only one complex species was detected on the surface.

Metacyclogenesis modulates the ability of Leishmania promastigotes to induce IL-12 production in human mononuclear cells

Immunity against the intracellular protozoan Leishmania species is highly dependent on Th1 development. We have previously shown that IL-12 is a powerful and probably obligatory factor for Th1 cell generation and proliferation. We also observed that the experimental infection of C3H and BALB/c mice with Leishmania major is associated with IL-12 production in vivo. Now we demonstrate that metacyclic L. major promastigotes are poor inducers of IL-12 in vitro in fresh human PBMC and monocytes. In addition, we show that the ability of this pathogen to induce IL-12 and other cytokines is modulated by the metacyclogenic process, which had previously not been recognized. In contrast to the infective parasites (metacyclic promastigotes), the procyclic promastigotes collected at the logarithmic phase of the culture displayed a striking ability to induce IL-12, IFN-γ, TNF-α, and IL-10. Despite this differential effect of procyclic and metacyclic parasites in terms of IL-12 induction, both stages were inhibitory for IL-12 production induced by Staphylococcus aureus. The ability of procyclic promastigotes and, to a much lesser extent, that of metacyclic promastigotes to induce IL-12 were enhanced by pretreatment of monocytes in a cytokine milieu containing IFN-γ, IL-4, IL-13, or granulocyte-macrophage CSF or. by neutralization of endogenous IL-10. Our results suggest the development of an evasion mechanism as the Leishmania promastigotes mature to infectious forms and the possi-bility of using Ags derived from procyclic promastigotes for immunization procedures. Copyright © 1997 by The American Association of Immunologists.

Interaction of mercury(II) with humic substances from the Rio Negro (Amazonas State, Brazil) by means of an ion exchange procedure

The aquatic humic substances (HS) investigated in this study with respect to their binding capability towards mercury(II) were isolated from the river Rio Negro, Amazonas State - Brazil, by means of the adsorbent XAD 8. Labile/inert fractions of inorganic Hg(II) complexes formed with these HS were characterized using an ion-exchange batch and column technique, respectively, based on Chelite S. This collector exhibits high Hg(II) distribution coefficients, Kd, up to the order of 104 decreasing, however, in the case of small Hg(II)/HS ratios (< 0.1 μg Hg(II) / mg HS). The influence of different complexation parameters (ratio of Hg(II)/HS, pH, contact time, complexing time) relevant for Hg(II) binding in aquatic environments was assessed. The Hg(II) lability in dissolved HS is mainly influenced by the mass ratio of Hg(II)/HS and the ageing of Hg(II)-HS species formed. This is particularly obvious in the case of low Hg(II) loading of HS where slow transformation processes of freshly formed Hg(II)-HS species significantly decrease their lability, leading to incomplete recoveries (< 20%) of the total Hg(II) bound to HS.

A description of ligand field effects in the Di-μ-Azido-Bis [{Azido(N,N-diethylethylenediamine)}Copper(II)] compound by the simple overlap model

We present a theoretical description of ligand field effects in the di-μ-azido- bis[{azido(N,N-diethylethylenediamine)} copper(II)] compound by the Simple Overlap Model. The ligand field Hamiltonian is expressed in terms of irreducible tensor operators for an assumed D3h site symmetry occupied by the copper ion. The ligand field parameters, calculated from the available structural data, indicate that the copper ion is under the influence of a very strong ligand field. The energy of the d-d absorption band is well reproduced phenomenologically by the model.

Tetradentate schiff base copper(II) complexes

Ten copper(II) complexes of tetradentate Schiff bases obtained by condensing two moles of an o-hydroxyphenylcarbonyl compound with a diamine have been prepared and characterized by elemental analyses, melting points, IR and electronic spectra. The IR and electronic spectra of the free ligand and the complexes are compared and discussed. The deconvolution of the visible spectra of the complexes in CHCl3, approximately C2v or C1, yielded four peaks at ca. 15000, 17000, 18000-19000, and 20000-22000 cm-1, assigned to the four d-d transitions.

Tipos de resistência a Alabama Argillacea (Huebner, 1818) (Lepidoptera: Noctuidae) envolvidos em genótipos de algodoeiro: II. Antibiose

Cotton genotypes resistance to Alabama argillacea (Huebner, 1818) due to antibiosis has been evaluated in laboratory trials (at 27 ± 2°C, 70 ± 10% relative humidity and 14 hours photoperiod). Six different genetic materials (T 1122-13-1, STO 285 N, JPM 157, T 953-13-4-2, CNPA 9211-21, and CNPA 9211-31) have been tested in a completely randomized experimental design, with ten replications, each one with ten larvae/genotype. Larvae have been supplied with leaves daily. The following variables have been scored: time length of several insect stages (from larvae to adult), average mass of larvae and pupae as well as average larval, pre-pupal and pupal mortality rates. All genotypes have revealed longer overall average time length of stage duration from larvae to adult, as compared to STO 285 N; however, CNPA 9211-31 and CNPA 9211-21 have shown the smallest average mass of pupae along with high frequencies of pre-pupae and larvae to adult mortalities. The results strongly suggest that antibiosis is one of the resistance mechanisms to A. argillacea in that two cotton genotypes.

IL-12 and neutralization of endogenous IL-10 revert the in vitro antigen-specific cellular immunosuppression of paracoccidioidomycosis patients

Treatment of patients with paracoccidioidomycosis is still a challenge. Patients present defective lymphoproliferation and IFN-γ responses to the main Paracoccidioides brasiliensis antigen (gp43), which correlates with disease severity. Here, we demonstrated that the patients show also a defective synthesis of interleukin (IL)-12. Therefore, we attempted to revert this immune disfunction by adding IL-12 and neutralizing anti-IL-10 antibody to gp-43-stimulated peripheral blood mononuclear cell cultures. Both treatments increased IFN-γ secretion to levels observed with healthy sensitized individuals, but affected proliferation only modestly. When combined, the treatments further increased IFN-γ synthesis and cell proliferation. The addition of suboptimal concentrations of IL-2 also further increased the IL-12-mediated secretion of IFN-γ. Interestingly, the immune modulation was mostly antigen-specific, since the responses to Candida albicans' antigen were not affected. These results suggest that appropriate immune intervention with cytokines and/or anti-cytokines may help in the treatment of PCM. © 2002 Elsevier Science Ltd. All rights reserved.

Crystal structure of di-μ(N,S)-thiocyanato-bis[(N-benzylideneaniline-C 2,N)palladium(II)], [Pd(C6H4CH=NC 6H5)(μ-SCN)]2

C28H20N4Pd2S2, monoclinic, P121/c1 (No. 14), a = 11.325(1) Å, b = 13.530(1) Å, c = 17.925(1) Å, β = 106.23(1)°, V = 2637.1 Å 3, Z = 4, Rgt(F) = 0.052, wRref(F2) = 0.129, T = 293 K. © by Oldenbourg Wissenschaftsverlag.