An EPR and optical absorption study of VO2+ ions in di-ammonium hydrogen citrate [(NH4)2C6H6O7] single crystals

Single crystal and powder EPR studies of VO2+ doped di-ammonium hydrogen citrate [(NH4)2C6H6O7] are carried out at room temperature. The angular variation of the EPR spectra show three different VO2+ complexes that are located in different chemical environment, and each environment contains two magnetically inequivalent VO2+ sites in distinct orientations occupying substitutional positions in the lattice. Crystalline field around the VO2+ ion is nearly axial. The optical absorption spectrum shows two bands centred at 16,949 and 12,345cm(-1). Spin Hamiltonian parameters and molecular orbital coefficients are calculated from the EPR and optical data, and results are discussed.     

EPR and optical absorption studies of VO2+ doped L-arginine phosphate monohydrate single crystals--part I.

The electron paramagnetic resonance (EPR) studies on VO2+ doped L-arginine phosphate monohydrate (LAP) single crystals at room temperature at X-band frequencies reveal the presence of two magnetically inequivalent VO2+ sites occupying interstitial positions in the lattice with fixed orientations and show very high angular dependence. The principal values of the g and A tensors indicate that the electrostatic field around the VO2+ ion is rhombic. The optical absorption spectra at room temperature show four absorption bands at 16155, 14775, 10928 and 10526 cm(-1), characteristic of rhombic symmetry. From EPR and optical absorption data, the molecular orbital bonding coefficients (beta2, epsilon2, P and k) and the crystal field parameters have been evaluated.     

VO2+ ions in zinc lead borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of vanadyl ions in zinc lead borate (ZnO-PbO-B2O3) glass system have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of VO2+ ions. The values of spin-Hamiltonian parameters indicate that the VO2+ ions in zinc lead borate glasses were present in octahedral sites with tetragonal compression and belong to C4V symmetry. The spin-Hamiltonian parameters g and A are found to be independent of V2O5 content and temperature but changing with ZnO content. The decrease in Deltag( parallel)/Deltag( perpendicular) value with increase in ZnO content indicates that the symmetry around VO2+ ions is more octahedral. The decrease in intensity of EPR signal above 10 mol% of V2O5 is attributed to a fall in the ratio of the number of V4+ ions (N4) to the number of V5+ ions (N5). The number of spins (N) participating in resonance was calculated as a function of temperature for VO2+ doped zinc lead borate glass sample and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility was calculated at various temperatures and the Curie constant was evaluated from the 1/chi-T graph. The optical absorption spectra show single absorption band due to VO2+ ions in tetragonally distorted octahedral sites.     

Investigations of the optical and EPR spectra for VO2+ in LiKSO4 crystals

The optical spectra and EPR spectra (characterized by the spin-Hamiltonian parameters g(//), g(perpendicular), A(//) and A(perpendicular)) for the molecular ion VO2+ in LiKSO4 crystals are calculated from two microscopic theory methods, one of which is the complete diagonalization (of energy matrix) method (CDM) and the other is the perturbation theory method (PTM). The calculated three optical absorption bands and four spin-Hamiltonian parameters from the two methods are not only close to each other, but also in reasonable agreement with the experimental values. It appears that both theoretical methods are effective in the explanation of optical and EPR spectra for 3d1 ions in crystals. The negative signs of hyperfine structure constants A(//) and A(perpendicular) for VO2+ in LiKSO4 crystals are also suggested from the calculations.     

EPR and optical studies of vanadium doped potassium dihydrogen citrate (C6H7KO7) single crystal

An EPR and optical studies of VO2+ doped potassium dihydrogen citrate (PDHC) single crystals have been carried out at room temperature. It crystallizes in triclinic symmetry with the unit cell dimensions: a=11.343?, b=13.078?, c=6.272?, α=89.79°, β=94.36°, γ=104.2°. The angular variation of EPR spectra have shown that two different VO2+ complexes are located in different chemical environments and each environment contains one magnetically VO2+ site occupying substitutional position in the lattice and show very high angular dependence.     

Single crystal EPR and optical absorption studies of Cu2+ ion in L-arginine sulphophosphate monohydrate--a nonlinear optical crystal

The EPR spectra of Cu2+ ion in L-arginine sulphophosphate monohydrate (LASP), a nonlinear optical material (NLO) have been studied at room temperature. Two magnetically inequivalent interstitial Cu2+ sites in the lattice were identified. The principal values of g- and A-tensors indicate that the symmetry of the electrostatic field around the Cu2+ ion is rhombic. Bonding parameters have been evaluated and the ground state wave function of Cu2+ ion is constructed. The ground state is found to be an admixure of x2 - y2 and 3z2 - r2 orbitals. By correlating EPR and optical absorption spectra the crystal field parameters have been evaluated.     

Vanadium-binding protein in a vanadium-rich ascidian Ascidia sydneiensissamea: CW and pulsed EPR studies

Some of the ascidians belonging to the suborder Phlebobranchia accumulate vanadium ion efficiently from seawater. Clarification of the mechanism of this surprisingly efficient metal-accumulation system is desirable. Two mutually similar vanadium-binding proteins (vanabin1 and vanabin2) have recently been isolated from a vanadium-rich ascidian Ascidia sydneiensis samea. In this study, the vanadium-binding properties of vanabin2 have been investigated by X-band CW EPR and pulsed EPR spectroscopy. CW EPR spectra of samples containing various ratios of VO2+ and vanabin2 invariably exhibited a usual mononuclear-type VO2+ EPR signal with the intensity dependent on the ratio [vanabin]/[V]. EPR titration has shown that vanabin2 can bind up to approximately 23.9 vanadium ions per one molecule, almost all of which ( approximately 84%) are in a mononuclear VO2+ state as estimated by EPR quantitation. Electron spin-echo envelope modulation (ESEEM) spectra of VO-vanabin2 exhibited reasonably intense peaks attributable to amine nitrogen. This is consistent with the fact that vanabin2 is a lysine-rich protein (14 lysines out of 91 amino acids). The present study reveals the uniqueness of vanabin2, which can bind a large number of metal ions in a mononuclear fashion in contrast to the situation for ferritin and metallothionein.     

Spectroscopic and structural characterization of pascoite

Pascoite mineral having yellow-orange colour of Colorado, USA origin has been characterized by EPR, optical and NIR spectroscopy. The colour dark red-orange to yellow-orange colour of the pascoite indicates that the mineral contain mixed valency of vanadium. The optical spectrum exhibits a number of electronic bands due to presence of VO(II) ions in the mineral. From EPR studies, the parameters of g, A are evaluated and the data confirm that the ion is in distorted octahedron. Optical absorption studies reveal that two sets of VO(II) is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules.     

Structural investigations on sodium-lead borophosphate glasses doped with vanadyl ions

Electron paramagnetic resonance (EPR), optical absorption, and FT-IR spectra of vanadyl ions in the sodium-lead borophosphate (Na(2)O-PbO-B(2)O(3)-P(2)O(5)) (SLBP) glass system have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of VO(2+) ions. The spin Hamiltonian parameters g and A are found to be independent of the V(2)O(5) content and temperature. The values of the spin Hamiltonian parameters indicate that the VO(2+) ions in SLBP glasses are present in octahedral sites with tetragonal compression. The population difference between Zeeman levels (N) is calculated as a function of temperature for an SLBP glass sample containing 1.0 mol % VO(2+) ions. From the EPR data, the paramagnetic susceptibility (χ) is calculated at different temperatures, and the Curie constant (C) is calculated from the 1/χ versus T graph. The optical absorption spectra of the glass samples show two absorption bands, and they are attributed to V(3+) and V(4+) ions. The optical band gap energy (E(opt)) and Urbach energy (ΔE) are calculated from their ultraviolet absorption edges. It is observed that, as the vanadium ion concentration increases, E(opt) decreases and ΔE increases. The study of the IR absorption spectrum depicts the presence of BO(3), BO(4), PO(3), PO(4), and VO(5) structural units.     

EPR of vanadyl ion in a natural mineral, apophyllite

Single crystal EPR spectra of a natural mineral, apophyllite, containing VO(II) ion as an impurity have been investigated. The EPR spectra of the mineral, as obtained, was complex in nature, but was simplified by annealing the crystals at 490 K. The EPR parameters of the VO(II) species in the annealed crystal,g _∥ = 1.924 (2);g _⊥ = 1.983 (2);A _∥ = 18.35 (5); andA _⊥ = 7.24 (5)mT, are very close to a typical VO(II) impurity. Theoretically calculated line positions, using second-order hyperfine terms in the spin Hamiltonian with an axially symmetricg andA tensor values, agreed very well with the experimental ones. The EPR analysis of the annealed crystal has further revealed that the most preferred location of the VO(II) impurity is a substitutional Ca(II) site. The calculated bonding parameters and admixture coefficients indicate a fair amount of covalent bonding in the complex.     

EPR of VO2+ in double format, Ba2Zn(HCOO)6(H2O)4 single crystals

VO(2+) doped single crystal of Ba(2)Zn(HCOO)(6)(H2O)(4) (BZFA) were investigated using electron paramagnetic resonance (EPR) technique at ambient temperature. Detailed investigation of EPR spectra indicated that the VO(2+) substitutes the Zn(2+) in the structure. The sites with different orientations were observed for VO(2+) in Ba(2)Zn(HCOO)(6)(H2O)(4).single crystal, but the only intense site among these sites was evaluated to obtain spin-Hamiltonian parameters, which are the principal axis values of the g and the hyperfine tensors. The covalent bonding parameter for VO(2+) and Fermi contact term were calculated using the spin-Hamiltonian parameters.     

Synthesis, crystal structures, and properties of oxovanadium(IV)-lanthanide(III) heteronuclear complexes

A new series of oxovanadium(IV)-lanthanide(III) heteronuclear complexes [Yb(H2O)8]2[(VO)2(TTHA)](3)21 H2O (1), {[Ho(H2O)7(VO)2(TTHA)][(VO)2(TTHA)](0.5)} 8.5 H2O (2), {[Gd(H2O)7(VO)2(TTHA)][(VO)2(TTHA)](0.5)}8.5 H2O (3), {[Eu(H2O)7][(VO)2(TTHA)](1.5)} 10.5 H2O (4), and [Pr2(H2O)6(SO4)2][(VO)2(TTHA)] (5) (H6TTHA=triethylenetetraaminehexaacetic acid) were prepared by using the bulky flexible organic acid H(6)TTHA as structure-directing agent. X-ray crystallographic studies reveal that they contain the same [(VO)2(TTHA)]2- unit as building block, but the Ln3+ ion lies in different coordination environments. Although the lanthanide ions always exhibit similar chemical behavior, the structures of the complexes are not homologous. Compound 1 is composed of a [Yb(H2O)8]3+ ion and a [(VO)2(TTHA)]2- ion. Compounds 2 and 3 are isomorphous; both contain a trinuclear [Ln(H2O)7(VO)2(TTHA)]+ (Ln=Ho for 2 and Gd for 3) ion and a [(VO)2(TTHA)]2- ion. Compound 4 is an extended one-dimensional chain, in which each Eu3+ ion links two [(VO)2(TTHA)]2- ions. For 5, the structure is further assembled into a three-dimensional network with an interesting framework topology comprising V2Pr2 and V4Pr2 heterometallic lattices. Moreover, 4 and 5 are the first oxovanadium(IV)-lanthanide(III) coordination polymers and thus enlarge the realm of 3d-4f complexes. The IR, UV/Vis, and EPR spectra and the magnetic properties of the heterometallic complexes were studied. Notably, 2 shows unusual ferromagnetic interactions between the VO2+ and Ho3+ ions.     

EPR and optical absorption studies of Cu2+ doped L-arginine phosphate monohydrate single crystals--part II

The EPR spectra of Cu2+ ion in L-Arginine phosphate monohydrate (LAP) at X-band frequencies at room temperature reveal the presence of two magnetically inequivalent interstitial Cu2+ sites in the lattice. The principal values of the g- and A-tensors indicate rhombic symmetry around the Cu2+ ion. From the direction cosines of the principal values of the g- and A- tensors, the orientations of the sites in the lattice have been identified. The bonding parameters were evaluated and the ground state wave function of Cu2+ ion was constructed. The ground state is found to be an admixture of [x2 - y2> and [3z2 - r2> orbitals. The optical absorption studies show four bands centered at 9803, 10753, 15748 and 16666 cm(-1) confirming the rhombic symmetry around the Cu2+ ion. Using the observed bands the crystal field parameters have been evaluated.     

EPR spectra of Cu2+ and VO2+ ions in ammonium hydrogen oxalate hemihydrate [(NH4)HC2O4 . (1/2)H2O] single crystals

Cu(2+) and VO(2+) doped ammonium hydrogen oxalate hemihydrate, [(NH(4))HC(2)O(4) . (1/2)H(2)O], single crystals have been studied at room temperature and at 113K in three mutually perpendicular planes. Both ions yield unexpectedly large number of lines. The calculated results of the Cu(2+) and VO(2+) doped in [(NH(4))HC(2)O(4) . (1/2)H(2)O] indicate that both ions substitute with the NH(4)(+) ion in the structure. The EPR spectra of Cu(2+) ions are characteristic of tetragonally elongated octahedral site and the spectra of VO(2+) are characteristic of tetragonally compressed complex. The angular variation of the EPR spectra has shown that two different Cu(2+) and VO(2+) complexes are located in different chemical environments, and each environment contains two magnetically inequivalent Cu(2+) and VO(2+) sites in distinct orientations occupying substitutional positions in the lattice and show very high angular dependence. The principal g and the hyperfine (A) values of both ions are determined.     

Optical absorption and EPR studies on some natural carbonate minerals

Limestone and dolomite minerals have been investigated by EPR and optical absorption studies. The optical absorption results indicate the presence of ferrous and ferric ion in both the minerals. The bands observed at 24,750, 22,780, 19,415 and 14,450cm(-1) are assigned to 6A1-->4T2 (4D), 6A1-->4E, 4A1 (4G), 6A1-->4T2 (4G) and 6A1-->4T1 (4G) d-d transitions of Fe3+ ions, respectively. A low energy band at 10,638cm(-1) is identified as being due to Fe2+ ion and can be attributed to 5T2g-->5E(g) transition. The weak band in the region 30,000-40,000cm(-1) corresponds to Fe-O charge transfer. Crystal field and Racah parameters evaluated for the Fe2+ ion are Dq=990cm(-1), B=885cm(-1) and C=3860cm(-1) and that for Fe3+ ions are Dq=1040cm(-1), B=703cm(-1) and C=3150cm(-1). The room temperature 9 and 35GHz EPR spectra of the minerals exhibit a sextet hyperfine pattern characteristic of Mn2+. The EPR parameters obtained for Mn2+ in limestone are g=2.00399, A= -9.411mT, D= -8.19mT and these values confirm that the Mn2+ ion are located in the calcite impurity. For Mn2+ in dolomite are g=2.0004, A= -9.45mT for Mn2+ substituted in the Ca lattice site and g=2.00984, A= -9.37mT, D= -9.94mT for substitution at the Mg site. The EPR spectra of heat-treated limestone and dolomite samples at 950 degrees C show a signal corresponding to CO2(-) ion.     

EPR and IR spectral studies of the sea water mussel Mytilus conradinus shells

The electron paramagnetic resonance (EPR) and infrared (IR) spectral studies have been employed on the periostracum, the prismatic layer and the nacre of the shell of the marine bivalve molluscan Mytilus conradinus of the South Indian origin. All the layers of this shell show Fe3+ ion spin resonance signals in common. The inner layer namely nacre at room temperature shows EPR signals of Fe3+ ions and the heated one exhibits a sextet hyperfine pattern characteristic of Mn2+ ions. The prismatic layer of the shell also exhibits a similar spectrum, but of distinct pattern. The spin-Hamiltonian parameters have been evaluated for the prismatic and nacreous layers of this shell. Infrared spectra of the two main layers of the shell namely prismatic and the nacre exhibit the characteristic bands of CO3(2-) molecular ion in different symmetries of CaCO3.     

Electron Paramagnetic Resonance and optical absorption spectra of Cr3+ in zinc maleate tetrahydrate single crystals

Electron Paramagnetic Resonance (EPR) and optical absorption spectra of Cr³⁺ ions doped in single crystals of zinc maleate tetrahydrate (ZMTH) have been studied at room temperature (300 K). The EPR spectra exhibit a group of three fine structure transitions, characteristic of the Cr³⁺ ion. From the observed EPR spectra, the spin-Hamiltonian and zero-field splitting parameters have been determined. The optical absorption spectrum exhibits two broad bands characteristic of Cr³⁺ ions in octahedral symmetry. From the observed spectrum, the crystal field parameters have been evaluated.     

Monosaccharides and the VO(IV) metal ion: Equilibrium,thermal studies and hypoglycemic effect

Protonation and complexation equilibriums of monosaccharides and the VO(IV) metal ion in aqueous solution were studied as well as their effect on the hyperglycemia of diabetic rats. The complexes formed were characterized by potentiometric titrations, paramagnetic resonance spectroscopy (EPR) and thermogravimetric–differential scanning calorimetry (TGA–DSC). The system involving d-gluconic acid (HGlu) and oxovanadium(IV) (VO²⁺) was chosen to study the serum glucose levels in alloxan-induced diabetic rats. A binuclear species was detected in small quantities, which was formed by coordination of two HGlu molecules and two VO²⁺ ions through a hydroxide bridge. The mononuclear species formed by HGlu and VO²⁺ were confirmed by EPR. The anisotropic spectra obtained from aqueous frozen solutions (77 K) are characteristic of mononuclear VO-hexoses. The cyclic sugars d-ribone-1,4-lactone (Riblac), d-galactone-1,4-lactone (Galac) and 2-deoxy-d-glucopyranose (dGlu) showed weak interactions with the metal ion and they are not able to hold the metal in solution above pH 4.6 resulting in hydrolysis of the metal ion. Also, the acute treatment with sugar complexes of HGlu–VO led to a significant hypoglycemic effect (23% and 18% by intraperitoneal or oral gavage treatment, respectively) in diabetic rats. These results show the potential effectiveness of VO–HGlu complexes as anti-hyperglycemic agents through intraperitoneal injection in alloxan-induced diabetic rats.     

Studies of EPR parameters for Mn5+ -doped Li3PO4 and Li3VO4 crystals

The EPR parameters (zero-field splitting D and g factors g parallel, g perpendicular) of Mn5+ -doped Li3PO4 and Li3VO4 crystals are calculated from the complete high-order perturbation formulas based on a molecular orbital scheme for a 3d2 ion in tetragonal MX4 clusters. These formulas include not only the contribution coming from crystal-field excitations, but also that arising from charge-transfer excitations (which is discarded in crystal field theory). The calculated results are in reasonable agreement with the observed values. The contributions to EPR parameters coming from the charge-transfer excitations are comparable with those arising from the crystal-field excitations. It appears that for a high valence state 3dn ion in crystals, the reasonable explanations of EPR parameters should take the contributions due to both crystal-field and charge-transfer excitations into account.     

Chemistry and insulin-mimetic properties of bis(acetylacetonate)oxovanadium(IV) and derivatives

The syntheses and the solid state structural and spectroscopic solution characterizations of VO(Me-acac)2 and VO(Et-acac)2 (where Me-acac is 3-methyl-2,4-pentanedionato and Et-acac is 3-ethyl-2,4-pentanedionato) have been conducted since both VO(acac)2 and VO(Et-acac)2 have long-term in vivo insulin-mimetic effects in streptozotocin-induced diabetic Wistar rats. X-ray structural characterizations of VO(Me-acac)2 and VO(Et-acac)2 show that both contain five-coordinate vanadium similar to the parent VO(acac)2. The unit cells for VO(Et-acac)2 and VO(Me-acac)2 are both triclinic, P1, with a = 9.29970(10) A, b = 13.6117(2) A, c = 13.6642(2) A, alpha = 94.1770(10) degrees, beta = 106.4770(10) degrees, gamma = 106.6350(10) degrees for VO(Et-acac)2 and a = 7.72969(4) A, b = 8.1856(5) A, c = 11.9029(6) A, alpha = 79.927(2) degrees, beta = 73.988(2)degrees, gamma = 65.1790(10)degrees for VO(Me-acac)2. The total concentration of EPR-observable vanadium(IV) species for VO(acac)2 and derivatives in water solution at 20 degreesC was determined by double integration of the EPR spectra and apportioned between individual species on the basis of computer simulations of the spectra. Three species were observed, and the concentrations were found to be time, pH, temperature, and salt dependent. The three complexes are assigned as the trans-VO(acac)2.H2O adduct, cis-VO(acac)2.H2O adduct, and a hydrolysis product containing one vanadium atom and one R-acac- group. The reaction rate for conversion of species was slower for VO(acac)2 than for VO(malto)2, VO(Et-acac)2, and VO(Me-acac)2; however, in aqueous solution the rates for all of these species are slow compared to those of other vanadium species. The concentration of vanadium(V) species was determined by 51V NMR. The visible spectra were time dependent, consistent with the changes in species concentrations that were observed in the EPR and NMR spectra. EPR and visible spectroscopic studies of solutions prepared as for administration to diabetic rats documented both a salt effect on speciation and formation of a new halogen-containing complex. Compound efficacy with respect to long-term lowering of plasma glucose levels in diabetic rats traces the concentration of the hydrolysis product in the administration solution.