Luminescence study of LiMgBO3 :Dy for γ-ray and carbon ion beam exposure.

LiMgBO3 :Dy3+ , a low Zeff material was prepared using the solution combustion method and its luminescence properties were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), thermoluminescence (TL), photoluminescence (PL), Fourier transform infrared spectroscopy, and electron paramagnetic resonance (EPR) techniques. Reitvield refinement was also performed for the structural studies. The PL emission spectra for LiMgBO3 :Dy3+ consisted of two peaks at 478 due to the 4 F9/2 →6 H15/2 magnetic dipole transition and at 572 nm due to the hypersensitive 4 F9/2 →6 H13/2 electric dipole transition of Dy3+ , respectively. A TL study was carried out for both the γ-ray-irradiated sample and the C5+ irradiated samples and was found to show high sensitivity for both. Moreover the γ-ray-irradiated LiMgBO3 :Dy3+ sample showed linearity in the dose range 10 Gy to 1 kGy and C5+ -irradiated samples show linearity in the fluence range 2 × 1010 to 1 × 1011 ions/cm2 . In the present study, the initial rise method, various heating rate method, the whole glow curve method, glow curve convolution deconvolution function, and Chen's peak shape method were used to calculate kinetic parameters to understand the TL glow curve mechanism in detail. Finally, an EPR study was performed to examine the radicals responsible for the TL process.

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy.

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr2CeO4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr2CeO4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, impedance spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr2CeO4 which has tendency to decompose peritectically to SrCeO3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr2CeO4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO66- (octahedral uranate) in Sr2CeO4. Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr2CeO4 and it has two different environments due to its stabilization at both Sr2+ as well as Ce4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr2CeO4 based optoelectronic material as well exploring it for actinides studies.

On the study of the C6+ ion beam and γ-ray induced effect on structural and luminescence properties of Eu doped LiNaSO4: explanation of TSL mechanism using PL, TL and EPR study.

The present paper reports on the γ-ray and C6+ ion beam induced effect on the structural and luminescence properties of Eu doped LiNaSO4 phosphors synthesized via wet the chemical method. The material was irradiated by 60Co and 137Cs γ-rays and 75 MeV C6+ ions in a fluence range varying from 2 × 1010 to 1 × 1012 ion per cm2. The ion induced modified properties were investigated using X-ray diffraction (XRD), micro-Raman spectroscopy, photoluminescence (PL), thermoluminescence (TL) and electron paramagnetic resonance (EPR) studies. The XRD and micro-Raman results confirm the loss of crystallinity and elongation of the lattice parameters after ion beam irradiation. The presence of both divalent as well as trivalent states of Eu ions at multiple sites of LiNaSO4 is observed by PL study. Irradiation of the LiNaSO4:Eu phosphor with a C6+ ion beam modifies the population of the valence state of the doped rare earth Eu ion and enhances the TL sensitivity of this phosphor. The nature of the prominent TL glow curve is identical for both γ-ray and C6+ ion beam irradiated materials while additional deep trap levels appear in the latter due to the formation of several types of cation and anion vacancy. The electron paramagnetic resonance (EPR) technique also supports the presence of the Eu ion at multiple sites and provides information regarding several types of radical produced after γ-ray and C6+ ion irradiation. Finally, a mechanism is presented for the thermally stimulated luminescence phenomenon on the basis of our observed results from the PL, TL and EPR studies. The reason behind ion beam irradiation induced modification of the TL properties and enhancement of luminescence intensity is also explained in this report.

Defect induced ferromagnetism in MgO and its exceptional enhancement upon thermal annealing: a case of transformation of various defect states.

MgO particles of few micron size are synthesized through a sol-gel method at different annealing temperatures such as 600 °C (MgO-600), 800 °C (MgO-800) and 1000 °C (MgO-1000). EDX and ICP-AES studies confirmed a near total purity of the sample with respect to paramagnetic metal ion impurities. Magnetic measurements showed a low temperature weak ferromagnetic ordering with a TC (Curie temperature) around 65 K (±5 K). Unexpectedly, the saturation magnetization (Ms) was found to be increased with increasing annealing temperature during synthesis. It was observed that with J = 1 or 3/2 or S = 1 or 3/2, the experimental points are fitted well with the Brillouin function of weak ferromagnetic ordering. A positron annihilation lifetime measurement study indicated the presence of a divacancy (2VMg + 2VO) cluster in the case of the low temperature annealed compound, which underwent dissociations into isolated monovacancies of Mg and O at higher annealing temperatures. An EPR study showed that both singly charged Mg vacancies and oxygen vacancies are responsible for ferromagnetic ordering. It also showed that at lower annealing temperatures the contribution from was very low while at higher annealing temperatures, it increased significantly. A PL study showed that most of the F+ centers were present in their dimer form, i.e. as centers. DFT calculation implied that this dimer form has a higher magnetic moment than the monomer. After a careful consideration of all these observations, which have been reported for the first time, this thermally tunable unusual magnetism phenomenon was attributed to a transformation mechanism of one kind of cluster vacancy to another.

Melt-compounded composites of ethylene vinyl acetate with magnesium sulfate as flexible EPR dosimeters: Mechanical properties, manufacturing process feasibility and dosimetric characteristics.

Novel polymeric composites for radiation dosimetry were developed. The composites were prepared by solvent-free melt compounding of ethylene vinyl acetate (EVA) (40% vinyl) and magnesium sulfate (MgSO4). Mechanical properties, melt flow characteristics and dosimetric properties were investigated. The composites with up to 50% (wt) of MgSO4 were flexible and capable of flow. The dose response of the EPR signal of the composites was studied in the dose range 3Gy-4kGy and found to be linear between 18Gy and 4kGy. The reproducibility of dose measurements was good. The signal fading rate and the energy dependence of the dose response were found to be acceptable.

Understanding the complexation of Eu3+ with potential ligands used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle: A luminescence investigation.

A systematic photoluminescence based investigation was carried out to understand the complexation of Eu3+ with different ligands (TBP: tri-n-butyl phosphate, DHOA: di-n-hexyl octanamide, Cyanex 923: tri-n-alkyl phosphine oxide and Cyanex 272: Bis (2,4,4 trimethyl) pentyl phosphinic acid) used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle. In case of TBP and DHOA complexes, 3 ligand molecules coordinated in monodentate fashion and 3 nitrate ion in bidentate fashion to Eu3+ to satisfy the 9 coordination of Eu. In case of Cyanex 923 and Cyanex 272 complexes, 3 ligand molecules, 3 nitrate ion and 3 water molecules coordinated to Eu3+ in monodentate fashion. The Eu complexes of TBP and DHOA were found to have D3h local symmetry while that for Cyanex 923 and Cyanex 272 were C3h. Judd-Ofelt analysis of these systems revealed that the covalency of EuO bond followed the trend DHOA>TBP>Cyanex 272>Cyanex 923. Different photophysical properties like radiative and non-radiative life time, branching ratio for different transitions, magnetic and electric dipole moment transition probabilities and quantum efficiency were also evaluated and compared for these systems. The magnetic dipole transition probability was found to be almost independent of ligand field perturbation while electric dipole transition probability for 5D0-7F2 transition was found to be hypersensitive with ligand field with a trend DHOA>TBP>Cyanex 272>Cyanex 923.

Uranium luminescence in La2 Zr2 O7 : effect of concentration and annealing temperature.

The speciation of a particular element in any given matrix is a prerequisite to understanding its solubility and leaching properties. In this context, speciation of uranium in lanthanum zirconate pyrochlore (La2 Zr2 O7 = LZO), prepared by a low-temperature combustion route, was carried out using a simple photoluminescence lifetime technique. The LZO matrix is considered to be a potential ceramic host for fixing nuclear and actinide waste products generated during the nuclear fuel cycle. Special emphasis has been given to understanding the dynamics of the uranium species in the host as a function of annealing temperature and concentration. It was found that, in the LZO host, uranium is stabilized as the commonly encountered uranyl species (UO22+ ) up to a heat treatment of 500 °C at the surface. Above 500 °C, the uranyl ion is diffused into the matrix as the more symmetric octahedral uranate species (UO66- ). The uranate ions thus formed replace the six-coordinated 'Zr' atoms at regular lattice positions. Further, it was observed that concentration quenching takes place beyond 5 mol% of uranium doping. The mechanism of the quenching was found to be a multipolar interaction. Copyright © 2016 John Wiley & Sons, Ltd.

Photoluminescence and electron paramagnetic resonance properties of a potential phototherapic agent: MMgF4 :Gd3+ (M = Ba, Sr) sub-microphosphors.

Novel narrow band UVB-emitting phosphors, BaMgF4 :Gd3+ and SrMgF4 :Gd3+ phosphors, were synthesized using a co-precipitation synthesis method. X-Ray diffraction analysis was carried out to confirm compound formation, phase purity and crystallinity of the phosphor. At 274 nm excitation, phosphors show a sharp narrow band emission at 313 nm that can be assigned to 6 P7/2  â†’ 8 S7/2 transition of the Gd3+ ion. With increasing dopant concentration, intensity enhances and then decreases after a certain concentration, which is an indication of concentration quenching taking place in the phosphor. Scanning electron microscopy images of the phosphor show agglomerated particles in the sub-micron range. Particles range in size from 600 to 800 nm. Electron paramagnetic resonance studies of the phosphors were carried out to detect radicals present in the prepared phosphor. With narrow band UVB emission, phosphor seems to be a good candidate for UV phototherapy application. Copyright © 2016 John Wiley & Sons, Ltd.

Multifunctional pure and Eu(3+) doped ß-Ag2MoO4: photoluminescence, energy transfer dynamics and defect induced properties.

Pure and Eu(3+) doped ß-Ag2MoO4 were synthesized using a co-precipitation method at room temperature. The as prepared compounds were characterized systematically using X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, cyclic voltammetry (CV) and positron annihilation lifetime spectroscopy (PALS). It is observed that pure ß-Ag2MoO4 gives blue (445 nm) and green (550 nm) emission when irradiated with UV light. The origin of the green band was qualitatively explained from density functional theory (DFT) calculations using a suitable distortion model. It was observed that on doping europium ions, efficient energy transfer from molybdate to europium takes place. The excitation spectrum depicting f-f transitions (particularly 395 nm and 465 nm peaks) is much more intense than the CTB showing that Eu(3+) ions can be effectively excited by near UV-light. Based on DFT calculations it is proposed that due to the occurrence of Eu(3+) d-states in the conduction band (CB) as well as the strong contribution of Eu(3+) d-states to the impurity level present in the vicinity of the Fermi level, the host (ß-Ag2MoO4) to dopant (Eu(3+)) energy transfer is preferable. ß-Ag2MoO4 is also explored as a potential candidate for electrocatalysis of the oxygen reduction reaction (ORR). It was observed that the doping of europium ions in ß-Ag2MoO4 enhances the electrocatalytic activity toward the ORR. The presence of a large concentration of cation vacancies and large surface defects as suggested by positron annihilation lifetime spectroscopy (PALS) seem to be aiding the ORR.

Energy transfer dynamics and luminescence properties of Eu(3+) in CaMoO4 and SrMoO4.

Undoped and europium doped CaMoO4 and SrMoO4 scheelites are synthesized using a complex polymerization method. The phase purity of the sample is confirmed using powder X-ray diffraction (PXRD). X-ray photoelectron spectroscopy (XPS) was carried out to confirm the oxidation states of various constituents and dopant elements and also the presence of oxygen vacancies. Interestingly both CaMoO4 and SrMoO4 on irradiation with UV light give blue and green emission respectively. On europium doping, it was found that molybdate to Eu(3+) ion energy transfer is more efficient in SrMoO4:Eu compared to CaMoO4:Eu. It is also justified using a luminescence lifetime study which shows biexponential decay in the case of CaMoO4:Eu corresponding to both the host and europium ion; whereas a single lifetime is observed in the case of SrMoO4:Eu. Anomalies in host-dopant energy transfer are suitably explained using density functional theory (DFT) calculations and XPS. The actual site symmetry for the europium ion in CaMoO4 and SrMoO4 was also evaluated based on a Stark splitting pattern which turns out to be D2 and C2v respectively although it is S4 for Ca/Ba(2+) in AMoO4. This is also reflected in higher Ω2 values for SrMoO4:Eu than CaMoO4:Eu.

Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy.

A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P4(2)/mnm, a=4.5946(1) Å, c=2.9597(1) Å, V=62.48(1) (Å)(3), Z=2; anatase: space group I4(1)/amd, 3.7848(2) Å, 9.5098(11) Å, V=136.22(2) (Å)(3), Z=4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V(4+), Cr(3+), Mn(4+) and Fe(3+) species. EPR studies revealed the presence of transition metal ions V(4+)(d(1)), Cr(3+)(d(3)), Mn(4+)(d(3)) and Fe(3+)(d(5)) at Ti(4+) sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s>1) suggesting that the transition metal ions substitute the Ti(4+) in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S=3/2 and 5/2) are discussed.

Photoluminescence and EPR studies on Fe³âº doped ZnAl2O4: an evidence for local site swapping of Fe³âº and formation of inverse and normal phase.

Considering that ZnAl2O4 spinel has two different sites (octahedral and tetrahedral) and its properties change with dopant ion distribution among these two sites; ZnAl2O4 doped with varied concentrations of Fe(3+) was synthesized by a low temperature sol-gel combustion method. Phase purity and structural investigations were carried out using Rietveld refined X-ray diffraction which shows a decrease in the value of cell parameters at higher doping levels. Photoluminescence (PL) and electron paramagnetic resonance (EPR) studies have shown that on doping, Fe(3+) ions were distributed in both tetrahedral and octahedral sites. At octahedral sites, Fe(3+) exhibited a broad red emission around 745 nm while at tetrahedral sites it exhibited well-defined vibronic sidebands at 665, 674, 684 and 693 nm along with a broad blue band with a maxima at 445 nm at room temperature. EPR studies have shown a broad spectrum at g ≈ 2.2 which corresponds to the Fe(3+) in octahedral sites, while the broad signal at g ≈ 4.2 belongs to Fe(3+) in tetrahedral sites. It was also inferred from these studies that Fe(3+) prefers to occupy octahedral sites at higher concentrations and at higher annealing temperatures. The PL decay behavior of Fe(3+) in ZnAl2O4 has also shown that two different types of Fe(3+) ions were present in this matrix. The first type was a long lived species (τ ≈ 170 µs) present at octahedral sites and the other was a short lived species (τ ≈ 40 µs) present at the tetrahedral sites; the fraction of the long lived species predominate at higher concentrations. Thus the present work is mainly focused on understanding the tuning of local site occupancy of the dopant ion among those sites with varying concentration and annealing temperature, using the dopant ion itself as a spectroscopic probe, which further helps in understanding the phase (inverse and normal) of the spinel.

Influences of different environmental parameters on the sorption of trivalent metal ions on bentonite: batch sorption, fluorescence, EXAFS and EPR studies.

The presence of long-lived radionuclides in natural aquatic systems is of great environmental concern in view of their possible migration into biospheres of mankind. Trivalent actinides such as (241/243)Am can contribute a great deal to radioactivity for several thousand years. This migration is significantly influenced by various factors such as pH, complexing ions present in aquatic environments, and the sorption of species involving radionuclides by sediments around water bodies. Clay minerals such as bentonite are known to be highly efficient in radionuclide retention and hence are suitable candidates for backfill materials. This study presents experimental results on the interaction of Eu(iii) and Gd(iii) (chemical analogs of Am(iii) and Cm(iii)) with bentonite clay under varying experimental conditions of contact time, pH, and the presence of complexing anions such as humic acid (HA) and citric acid (cit). The sorption of HA on bentonite decreased with increasing the pH from 2 to 8, which was attributed to electrostatic interactions between HA and the bentonite surfaces. The sorption of Eu(iii) on bentonite colloids showed marginal variation with pH (>95%). However, a decrease in Eu(iii) sorption was observed in the presence of HA beyond pH 5 due to the increased aqueous complexation of Eu(iii) with deprotonated HA in the aqueous phase. The complexation of Eu(iii) with citrate ions was studied using Time Resolved Laser induced Fluorescence Spectroscopy (TRLFS) to explain the sorption data. Extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) investigations were carried out to understand the local chemical environment surrounding Eu(iii) and Gd(iii) (EPR probe) sorbed on bentonite under different experimental conditions. Surface complexation modelling shows the predominant formation of ≡XOEu(+2) (silanol) up to pH < 7, and beyond which ≡YOEu(OH)(+) (aluminol) is responsible for the quantitative sorption of Eu(iii) onto bentonite in the studied pH range.

Structural, luminescence and EPR studies on SrSnO3 nanorods doped with europium ions.

The present study describes the structural and luminescent properties of SrSnO(3) nanorods containing Eu(3+) ions. Based on Rietveld refinement of XRD patterns corresponding to both undoped and europium doped SrSnO(3) nanorods, it is inferred that the average bond lengths of Sr-O1 linkages, which have a square planar geometry around Sr(2+) in the SrO(12) polyhedra present in SrSnO(3), remained unaffected with Eu(3+) incorporation into the lattice. However, the average bond lengths of shorter Sr-O2 linkages increase and longer Sr-O2 linkages decrease with Eu(3+) doping into the SrSnO(3) lattice. A lack of variation in the lattice parameters of SrSnO(3) with doped Eu(3+) ions is explained based on mutually compensating changes in the average bond lengths of the Sr-O2 linkages in the unit cell. Luminescence studies have confirmed that Eu(3+) ions occupy the centrosymmetric Sr(2+) site only up to 2 at%, beyond which Eu(3+) ions exist in a significantly distorted environment (grain boundaries). Beyond 3%, incorporation of Eu(3+) ions into the SrSnO(3) lattice leads to the formation of a Eu(2)Sn(2)O(7) phase. From the EPR studies it is confirmed that around 5% of the incorporated Eu(3+) ions get converted to Eu(2+) ions and they occupy Sr(2+) sites in the lattice.

Rare examples of fluoride-based multiferroic materials in Mn-substituted BaMgF4 systems: experimental and theoretical studies.

A series of Mn-substituted BaMgF(4) samples have been synthesized by a hydrothermal route. X-ray diffraction study reveals that the products are monophasic in nature. Scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS) studies were carried out to investigate the morphology and stoichiometry for these compounds. X-ray photoelectron spectroscoy (XPS) and electron spin resonance (ESR) studies were done to confirm the oxidation state of dopant ion. Room temperature ferromagnetism was observed on Mn substitution at the Mg site in BaMgF(4) samples. The saturation magnetization increases initially, shows a peaking effect, and then decreases with further increase in Mn concentration in BaMg(1-x)Mn(x)F(4) (0.0 ≤ x ≤ 0.15). However, ferroelectricity was found to decrease with an increase in Mn concentration in the series of investigated BaMg(1-x)Mn(x)F(4) (0.0 ≤ x ≤ 0.15) samples. First-principle calculations, using the projector augmented wave potentials on Mn-substituted BaMgF(4), confirmed the decrease in magnetic moment with an increase in Mn content beyond certain concentration. These samples exhibit very weak magnetocapacitive coupling, which can be attributed to the very small magnetic signal observed in these samples.

EPR evidence for the restricted mobility of NO2 in gamma irradiated thorium nitrate pentahydrate Th(NO3)4·5H2O.

Electron paramagnetic resonance (EPR) studies were conducted on gamma irradiated polycrystalline sample of thorium nitrate pentahydrate, Th(NO(3))(4)·5H(2)O, in the temperature range of 100-300 K. The most prominent species with triplet hyperfine structure in the EPR spectrum was identified as NO(2). The EPR spectrum gave evidence for the stabilization of NO(2) in at least three different sites slightly differing in spin Hamiltonian parameters (Site(1): g(x)=2.0042, g(y)=1.9911, g(z)=2.0020, A(x)=54.20 G, A(y)=48.50 G and A(z)=65.25 G; Site(2): g(x)=2.0042, g(y)=1.9911, g(z)=2.0020, A(x)=54.20 G, A(y)=48.50 G and A(z)=67.85 G; Site(3): g(x)=2.0045, g(y)=1.9911, g(z)=2.0015, A(x)=54.20 G, A(y)=49.05 G and A(z)=72.45 G). The EPR spectra for Site(1) revealed molecular dynamics of NO(2) from a slow motion region to fast motion region as the sample temperature was varied from 100 to 300 K. This led to a change in EPR spectrum from orthorhombic to axial, indicating preferred rotation of NO(2) molecule about the O-O bond direction. However, the NO(2) molecule at Site(2) was found to be rigid throughout the entire temperature range. The differences in the mobility of NO(2) molecules occupying the two sites could be attributed to the fact that in one case NO(2) was bonded to thorium or water and in the other case it was weakly bound. The NO(2) bound to thorium through two oxygen atoms or bound to thorium on one side through one oxygen atom and hydrogen bonded to water on the other side remains rigid throughout the entire temperature range, while NO(2) situated at interstitial sites or adsorbed on the surface exhibits mobility with increase in temperature above 100K.

Effect of structure, particle size and relative concentration of Eu(3+) and Tb(3+) ions on the luminescence properties of Eu(3+) co-doped Y(2)O(3):Tb nanoparticles.

Eu(3+) co-doped Y(2)O(3):Tb nanoparticles were prepared by the combustion method and characterized for their structural and luminescence properties as a function of annealing temperatures and relative concentration of Eu(3+) and Tb(3+) ions. For Y(2)O(3):Eu,Tb nanoparticles annealed at 600 and 1200 °C, variation in the relative intensity of excitation transitions between the (7)F(6) ground state and low spin and high spin 4f(7)5d(1) excited states of Tb(3+) is explained due to the combined effect of distortion around Y(3+)/Tb(3+) in YO(6)/TbO(6) polyhedra and the size of the nanoparticles. Increase in relative intensity of the 285 nm peak (spin-allowed transition denoted as peak B) with respect to the 310 nm peak (spin-forbidden transition denoted as peak A) with decrease of Tb(3+) concentration in the Y(2)O(3):Eu,Tb nanoparticles heated at 1200 °C is explained based on two competing effects, namely energy transfer from Tb(3+) to Eu(3+) ions and quenching among the Tb(3+) ions. Back energy transfer from Tb(3+) to Eu(3+) in these nanoparticles is found to be very poor.

Synthesis and spectroscopic studies on copper(II) binuclear complexes of 1-phenylamidino-O-alkylurea (alkyl = n-propyl, n- and iso-butyl) with 1,3-diaminopropane or ethylenediamine.

Copper(II) binuclear complexes [Cu(II)(1-phenylamidino-O-n-propylurea)tn]2 (H2O)2(Cl2)2 (1), [Cu(II)(1-phenylamidino-O-n-butylurea)tn]2(H2O)2(Cl2)2(2), [Cu(II)(1-phenylamidino-O-i-butylurea)tn]2(H2O)2(Cl2)2(3), and [Cu(II)(1-phenyamidino-O-i-butylurea)en]2(H2O)2(Cl2)2 (4) have been reported. The binuclear complexes 3 and 4 crystallize in a monoclinic structure with unit cell dimensions a = 15.252(17) A, b = 14.682(10) A, c = 13.606(13) A, and beta = 111.2(1) degrees and a = 15.278(35) A, b = 14.665(21) A, c = 13.603(27) A, and beta = 111.1(1) degrees , respectively. The EPR spectra of all the solid complexes at room temperature consisted of fine-structure transitions (DeltaM(s) = 1) with zero-field splitting (ZFS) of 0.0500 cm(-1) and a half-field signal (DeltaM(s) = 2) at ca. 1600 G, suggesting the formation of binuclear complexes (S = 1). From the observed ZFS, we estimated the average Cu-Cu distance. From the temperature dependence of the EPR signal intensity, we evaluated the isotropic exchange interaction constant J. It appears that the exchange interaction between the two interacting spins of the binuclear complexes is ferromagnetic in nature. The formation of ferromagnetically coupled copper binuclear complexes was further confirmed from the high magnetic-moment values at room temperature. When the EPR spectra were recorded in the temperature range 300-400 K, it was observed that the triplet-state EPR signal completely and irreversibly disappeared at ca. 380 K with the appearance of a new signal attributable to the mononuclear complex (S = 1/2). Thermal studies of these complexes in this temperature range suggested the loss of two water molecules, which might be responsible for binding two mononuclear species. EPR, IR, and thermal studies indicate a long-range ferromagnetic exchange mediated through hydrogen bonding between copper(II) ions (S = 1/2).

Evaluation of a new copper(II)-curcumin complex as superoxide dismutase mimic and its free radical reactions.

A mononuclear (1:1) copper complex of curcumin, a phytochemical from turmeric, was synthesized and examined for its superoxide dismutase (SOD) activity. The complex was characterized by elemental analysis, IR, NMR, UV-VIS, EPR, mass spectroscopic methods and TG-DTA, from which it was found that a copper atom is coordinated through the keto-enol group of curcumin along with one acetate group and one water molecule. Cyclic voltammetric studies of the complex showed a reversible Cu(2+)/Cu(+) couple with a potential of 0.402 V vs NHE. The Cu(II)-curcumin complex is soluble in lipids and DMSO, and insoluble in water. It scavenges superoxide radicals with a rate constant of 1.97 x 10(5) M(-1) s(-1) in DMSO determined by stopped-flow spectrometer. Subsequent to the reaction with superoxide radicals, the complex was found to be regenerated completely, indicating catalytic activity in neutralizing superoxide radicals. Complete regeneration of the complex was observed, even when the stoichiometry of superoxide radicals was 10 times more than that of the complex. This was further confirmed by EPR monitoring of superoxide radicals. The SOD mimicking activity of the complex was determined by xanthine/xanthine oxidase assay, from which it has been found that 5 microg of the complex is equivalent to 1 unit of SOD. The complex inhibits radiation-induced lipid peroxidation and shows radical-scavenging ability. It reacts with DPPH radicals with rate constant 10 times less than that of curcumin. Pulse radiolysis-induced one-electron oxidation of the complex by azide radicals in TX-100 micellar solutions produced strongly absorbing ( approximately 500 nm) phenoxyl radicals, indicating that the phenolic moiety of curcumin remained intact on complexation with copper. The results confirm that the new Cu(II)-curcumin complex possesses SOD activity, free radical neutralizing ability, and antioxidant potential. Quantum chemical calculations with density functional theory have been performed to support the experimental observations.

EPR investigations on radiation induced chemical transformations in Pd(ClO4)2/i-PrOH/HClO4 system from 77 to 300 K.

The EPR studies have been carried out on gamma irradiated samples of Pd(ClO4)2 in 9 M/4M HClO4 in the presence and absence of isopropanol [i-PrOH (5%, v/v)], in the temperature range of 77-300 K. The EPR studies revealed the formation of Pd+ complex, Pd3+ complex and several radicals such as H., OH., ClO3., ClO4. and O3- on radiolysis of these systems. Reduction of Pd2+ to Pd clusters could not be observed in the absence of i-PrOH and warming of the irradiated sample finally resulted in recovery of Pd2+ complex. However, in the presence of 5% i-PrOH, strongly oxidizing radicals like OH., ClO3. and ClO4. are suppressed and (CH3)2C.OH radical was produced along with reducing species like H.. EPR spectra in these strongly reducing conditions showed formation of Pd+ complex, which on heating above 230 K, disproportionated into Pd0 and Pd2+ complex and finally lead to formation of Pd metal aggregates. Simultaneously, pulse radiolysis technique has been employed as an alternative method to verify the EPR observations.