EPR and magnetic susceptibility studies of the interaction between Cu2+ and Mn2+ ions in x(CuO·MnO)(1−x)[2B2O3·K2O] glasses

EPR and magnetic susceptibility experiments have been performed on x(CuO·MnO)(1?x)[2B₂O₃·K₂O] glasses with x varying in the range 0?x?50 mol.%. For x?3 mol.% both Cu²⁺ and Mn²⁺ ions are present mostly as the isolated species. The increase of the g-tensor values and bonding parameters (α², β², δ²) for Cu²⁺ ions together with the increase of TM ions concentration in the 0.2–1 mol.% range was noticed. In the case of 5 ? x ? 30 mol.% the dipole-dipole and superexchange interactions occur between transition metal ions, the first type of interactions prevailing in this range of concentration. For x30 mol.% the superexchange interaction prevail. The strong interaction between Cu²⁺ and Mn²⁺ gives rise to the exchange coupled Cu²⁺Mn²⁺ pairs in the studied glasses with x 3 mol.%.     

A cationic Rh(III) complex that efficiently catalyzes hydrogen isotope exchange in hydrosilanes

The synthesis and structural characterization of a mixed-sandwich (η(5)-C(5)Me(5))Rh(III) complex of the cyclometalated phosphine PMeXyl(2) (Xyl = 2,6-C(6)H(3)Me(2)) with unusual κ(4)-P,C,C',C' coordination (compound 1-BAr(f); BAr(f) = B(3,5-C(6)H(3)(CF(3))(2))(4)) are reported. A reversible κ(4) to κ(2) change in the binding of the chelating phosphine in cation 1(+) induced by dihydrogen and hydrosilanes triggers a highly efficient Si-H/Si-D (or Si-T) exchange applicable to a wide range of hydrosilanes. Catalysis can be carried out in an organic solvent solution or without solvent, with catalyst loadings as low as 0.001 mol %, and the catalyst may be recycled a number of times.     

ESR study of some Cu(II)-oxazepam complexes

The CuL₂X₂ (L = 7-chlor-l,3-dihydro-3-hydroxi-5-phenyl-2H-l,4-benzodiazepin-2-one, also known as oxazepam, X = Cl, Br) complexes were prepared and investigated by ESR (electron spin resonance) method. Powder ESR spectra of CuL₂X₂ compounds at room temperature show the presence of monomeric species having an axial symmetry with a small rhombic distortion. In case of compounds with Cl there is a superposition of two nonequivalent mononuclear species, one with ad_{x² - y²} d_{x^2 - y^2 } ground state and another with ad_z² d_{z^2 } ground state. In pyridine (Py) and dimethylformamide (DMF) solutions the monomeric species prevail. Two different monomeric species, one with pseudotetrahedral (T_d) and the other with elongated tetrahedral-octahedral symmetry, were evidenced in DMF solutions adsorbed on NaY zeolite. In Py-DMF solutions two monomeric species were also identified. Dimeric species appear in DMF and Py solutions adsorbed on NaY zeolite through the coordination of two Cu(II) ions at the same keto-oxygen from one oxazepam molecule.     

Magnetic properties of xCuO · (1 - x) [2B2O3 · PbO] glasses

The results of magnetic studies on xCuO · (1 ? x) [2B₂O₃ · PbO] glasses with 0 ? x ? 50 mol.%, are reported. These results evidenced that the copper ions, in this glass system, are in Cu²⁺ and Cu⁺ valence states. From Curie constant is determined the amount of the copper ions in bivalent state. For glasses with x > 5 mol.% CuO, an antiferromagnetic behaviour is evidenced.     

Gamma-ray spectrometric analysis of neutron irradiated golden sands

A nondestructive method has been used for the qualitative and quantitative determination of elements such as Au, Cu, Ag in minerals and especially in golden sand. The induced radioactivity has been analyzed with a high resolution gamma spectrometer containing a Ge(Li) semiconductor detector type and a multichannel analyzer. The samples have been collected from the alluvia of the Mure? and Some?ul Mic river basins, proving the presence of gold and copper in small concentrations. These results have been correlated to previous data showing the existence of some gold mines in these zones. This nondestructive, rapid and highly sensitive method can be used for industrial processes [1] control and prospections. The use of a NaI(Tl) scintillation crystal for routine measurements of the ¹⁹⁸Au radioisotope type and the interferences by copper, silver and indium in the irradiated samples are discussed.     

EPR investigations of Cu(II) complexes with 5′-CMP and 5′-GMP

Electron paramagnetic resonance investigation of the Cu(II) complexes with guanosine-5′-monophosphate (5′-GMP) and cytidine-5′-monophosphate (5′-CMP) shows the affinity of the Cu(II) ion to interact with the base and the phosphate group. The different modes of the coordination of the metal ion at the nucleotide and the water molecules lead to octahedral species, distorted by dynamical Jahn-Teller effect (g₀ = 2.106) for the Cu(II)-5′-CMP complex and rhombically distorted (g₁ = 2.358, g₂ = 2.126, g₃ = 2.068) or tetragonally distorted (g_∥^′ = 2.299, g_⊥^′ = 2.126) for the Cu(II)-5′ -GMP complex. The compound with 5′-CMP presents also a more stable in time square-planar species (g_∥ = 2.265, A_∥ = 162 G, g_⊥ = 2.076). The local symmetry changes in aqueous solution by coordination of water molecules.     

The local structure and interactions between V4+ ions in soda-phosphate glasses

EPR investigation on xV₂O₅ · (100 −x)[2P₂O₅ · Na₂O] and xV₂O₅ · (100 −x)[P₂O₅ · mNa₂O] (m = 1.5 and 2) glass systems was performed. The changes observed in the EPR spectra of xV₂O₅× (100 −x)[2P₂O₅ · Na₂O] glasses with increasing content of vanadium oxide are explained supposing that these spectra consist of two superposed EPR signals, one with hyperfine structure typical for isolated ions and another one consisting of a broad line without hyperfine structure characteristic for clustered ions. The clustered V⁴⁺ ions are not evidenced at low V₂O₅ contents (x = 5 mol%). The EPR spectra of xV₂O₅ · (100 −x)[P₂O₅ · mNa₂O] glasses indicate a superposition of two or three hyperfine structures attributed to nonequivalent VO²⁺ centers. Spin Hamiltonian parameters (g, A), dipolar hyperfine coupling parameter (P) and Fermi contact interaction term (K) have been evaluated. The ratio between the number of clustered and isolated ions was also determined.     

Prognostic role of genetic biomarkers in clinical progression of prostate cancer

The aim of this study was to analyze the use of 12 single-nucleotide polymorphisms in genes ELAC2, RNASEL and MSR1 as biomarkers for prostate cancer (PCa) detection and progression, as well as perform a genetic classification of high-risk patients. A cohort of 451 men (235 patients and 216 controls) was studied. We calculated means of regression analysis using clinical values (stage, prostate-specific antigen, Gleason score and progression) in patients and controls at the basal stage and after a follow-up of 72 months. Significantly different allele frequencies between patients and controls were observed for rs1904577 and rs918 (MSR1 gene) and for rs17552022 and rs5030739 (ELAC2). We found evidence of increased risk for PCa in rs486907 and rs2127565 in variants AA and CC, respectively. In addition, rs627928 (TT–GT), rs486907 (AG) and rs3747531 (CG–CC) were associated with low tumor aggressiveness. Some had a weak linkage, such as rs1904577 and rs2127565, rs4792311 and rs17552022, and rs1904577 and rs918. Our study provides the proof-of-principle that some of the genetic variants (such as rs486907, rs627928 and rs2127565) in genes RNASEL, MSR1 and ELAC2 can be used as predictors of aggressiveness and progression of PCa. In the future, clinical use of these biomarkers, in combination with current ones, could potentially reduce the rate of unnecessary biopsies and specific treatments.     

IR and ESR investigations on V2O5–P2O5–BaO glass system with opto-electronic potential

The changes observed in the IR and ESR spectra of the xV₂O₅(1 ? x)[0.8P₂O₅ ? 0.2BaO] glass system with 0 ≤ x ≤ 50 mol% show that vanadium oxide acts as a network modifier at low concentration (x ≤ 5 mol%) and as a network former for high content (x ≥ 10 mol%). Thus the IR bands belonging to the phosphate groups are strongly reduced except the specific bands of the short chain phosphate units due to the phosphate network depolymerization and the spectra are dominated by the vibrations characteristic for POP, POV and VOV linkages. At the same time the changes observed in the ESR spectra of these glasses are explained supposing the superposition of two signals, one with a well-resolved hyperfine structure typical for isolated V⁴⁺ ions and a broad line characteristic for clustered ions. The line width dependence versus V₂O₅ content shows that dipole–dipole interactions exist between vanadium ions until x = 5 mol% and the superexchange interactions prevail at high content (x > 10 mol%).     

Local structure analysis of Cu(II)-diazepam complexes by ESR spectroscopy

CuL₂X₂ (L = 7-chloro-1,3-dihydro-1-methyl-5-phenyl-3H-1,4-benzodiazepin-2-one, also known as diazepam, X = Cl, Br) complexes have been prepared and investigated by ESR spectroscopy. Powder ESR spectra of these complexes suggest a planar-rhombic distorted local symmetry. The CH₃Cl solutions spectra show the presence of pseudo-tetrahedral species with a 3d_xy+4p_z mixture ground state for the paramagnetic electron. The anisotropic spectra obtained for the Cu(II)-diazepam solution adsorbed on NaY zeolite confirm the existence of a CuN₂X₂ chromophore.