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The present study highlights the hazardous effect of heavy and light rare earth elements (REEs) on bovine liver catalase (BLC) using a combination of spectroscopic and computational methods. The presence of Praseodymium chloride (PrCl 3 ) and Gadolinium chloride (GdCl 3 ) resulted in a substantial reduction in catalytic efficiency of BLC by approximately 1.8 and 2.6 fold, respectively. The compromised activity was further accompanied by conformational rearrangements at the secondary and tertiary levels as evidenced by circular dichroism (CD) and fluorescence spectroscopy. These analyses revealed a significant decrease in α-helical content and a simultaneous increase in random coils, disrupting intramolecular hydrogen bonding. Furthermore, the zeta potential (ζ) of BLC demonstrated a reversal from negative to positive ζ values upon the addition of PrCl 3 and GdCl 3 , indicating BLC-lanthanide complex formation. Isothermal titration calorimetry (ITC) supports spontaneous interaction with negative free energy favouring endothermic reaction. This was further supported by docking studies which revealed the binding of PrCl 3 and GdCl 3 within the active site of BLC thus interfering with the catalytic ability to degrade hydrogen peroxide (H 2 O 2 ). Nevertheless, a significant decline in the melting temperature (T m ) of BLC was observed in the presence of lanthanides suggesting the thermal instability of the enzyme. Thus, a similar approach could be applied to evaluate the hazardous effects of lanthanides on structural and functional changes in other proteins or similar biomolecules., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Two new lanthanide complexes [PrL 2 (EA) 2 ]NO 3 (complex 1) and [SmL 2 (EA) 2 ]NO 3 (complex 2) (H 2 L = 5-(Pyrazol-1-yl)nicotinic acid, EA = CH 3 CH 2 OH) were synthesized. The structures were characterized by single crystal X-ray and elemental analysis. The interaction between the complex and fish sperm DNA(FS-DNA) was monitored using ultraviolet and fluorescence spectroscopy, and the binding constants were determined. Both complexes showed the ability to effectively bind DNA, and the molecular docking technology was used to simulate the binding of the complex and DNA. In addition, through the annexin V-Fluorescein Isothiocyanate(FITC)/ Propidium Iodide (PI) test experiment, tetrazollium [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT) in vitro test, and cell morphology apoptosis studies, it was shown that the complex can effectively induce HeLa tumor cell apoptosis. Compared with cisplatin and complex, complex 1 shows significant cancer cell inhibition, and we hope that this new type of complex will open up new ways for the next generation of drugs in biomedical applications., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The current study explores development of highly vascularizable biomatrix scaffold containing rare-earth metal praseodymium oxide nanoadditives for angiogenic and soft tissue regenerative applications. The therapeutic potential of praseodymium oxide nanoparticles rendered excellent endothelial cell differentiation for inducing pro angiogenic microenvironment by eliciting VE-Cadherin expression in the biomatrix scaffold. The nanoparticles were incorporated into bio-macromolecule collagen which aided in stabilization of collagen by maintaining the structural integrity of collagen and showed less susceptibility towards protease enzymes, high cyto-compatibility and high hemo-compatibility. The scaffold provided 3-dimensional micro-environments for the proliferation of endothelial cells and fibroblast cells promoting the wound healing process in an orchestrated fashion. Biological signal modulatory property of rare earth metal is the unexplored domains that can essentially bring significant therapeutic advancement in engineering advanced biological materials. This study opens potential use of nano-scaled rare earth metals in biomaterial application for tissue regeneration by modulating the pro-angiogenesis and anti-proteolysis properties., (Copyright © 2021 Elsevier Inc. All rights reserved.)

In a facile synthesis, highly colloidal, bioactive Pr(OH) 3 -encapsulated silica microspheres (PSMSs) with an average diameter of 500-700 nm were successfully prepared via a sol-gel process followed by heat treatment. The phase formation, morphology, surface and optical properties of the as-synthesized PSMSs were characterized by various techniques including X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), N 2 -adsorption-desorption, energy dispersive X-ray (EDX) analysis, Fourier transform infrared (FTIR) and UV/vis spectroscopy. The PSMSs were semi-amorphous or ultra-small in size, highly dispersible in water, mesoporous, irregular in size and spherical in shape. The SEM images show a well-ordered broad nanoporous structure which is preserved after coating with Pr(OH) 3 molecules, demonstrating interaction between the optically active Pr 3+ ion and silanol (Si-OH) groups via hydrogen bonding. Optical spectra show well-resolved weak intensity 4f-4f absorption transitions in the visible region of the Pr 3+ ion, indicating successful grafting of the Pr(OH) 3 layer. Toxicity was measured by MTT and NRU assays to determine potential toxicity. Cell viability was suppressed with increasing dosage of PSMSs, but showed greater than 55% cell viability at a concentration of 200 μg/mL, resulting in low toxicity. Due to its high aqueous dispersibility, optical activity, excellent biocompatibility and low toxic nature, it could be a favorable material for biomedical and drug delivery applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We used the condensation chemistry with anthracene‑9‑carbaldehyde and 3,4‑diaminopyridine to form Schiff base (SB) ligand, N 2 ,N 3 ‑bis (anthracen‑9‑ylmethylene) pyridine‑3,4‑diamine incorporating Er, Pr and Yb rare earth metals to form a series of SB complexes. Surface, structure, thermal, and optical properties of the resulting complexes were investigated using a variety of tools. The characteristic luminescence properties were observed after rare earth metal inclusions in SB. Antibacterial studies were performed against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa in terms of zone of inhibition for SB complexes. The SB-Pr complexes showed better immune behavior against all the pathogens than the other SB metal complexes., (Copyright © 2018. Published by Elsevier B.V.)

The Pr(3+)/Yb(3+) co-doped La2O3 and La(OH)3 nano-phosphors have been synthesized through solution combustion method. The structure and morphology of the samples have been studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The physical and optical properties of the samples have been measured and compared. A broad intense infrared emission centered at 850nm due to (1)I6→(1)G4 transition along with sharp green emission centerd at 513nm due to (3)P0→(3)H4 transition are observed on excitation with 976nm laser. The emission intensity of Pr(3+) is optimized with concentration and it is maximum at 0.08mol%. The annealed samples are found to be more crystalline and emit larger photoluminescence due to removal of quenching centers. The power dependent study of green upconversion emission indicates the involvement of two photons. The phosphor in La(OH)3 phase is more stable though the photoluminescence emission is slightly weak. La(OH)3 is less toxic compared to La2O3 and is biocompatible. It generates more heat and can be used in biothermal treatment., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Pd/CeO2-ZrO2-Pr2O3 (CZP) catalysts with different Ce/Zr molar ratios were synthesized and systematically investigated by XRD, N2 adsorption-desorption, XPS, H2-TPR, OSC and in situ DRIFTS techniques. The results of XPS, in situ DRIFTS, etc., show that the number of oxygen vacancies increases with the increasing Zr content and thus leads to the enhanced metal-support interaction and the accelerative formation rate of nitrate, formate, acetate and carbonate species, resulting in improving catalytic performance for HC and NO elimination, especially for Pd/CZP catalysts with Ce/Zr from 1/2 to 1/3. While Pd/CZP catalysts with higher OSC value (Ce/Zr=4/1-1/2) exhibit better catalytic activity of CO and NO2 elimination. An appropriate concentration of Zr facilitates the diffusion of Pr from the surface to the bulk of the CZP supports, thus forming more homogeneous CZP solid solution and improving the structure/textual stability, which promotes the thermal stability of catalysts. Pd/CZP catalysts with Ce/Zr from 2/1 to 1/2 exhibit good thermal stability., (Copyright © 2014 Elsevier B.V. All rights reserved.)

New fluorophore lanthanide complexes-Cloisite (LCs-C) nanohybrids have been prepared by the intercalation reaction of Cloisite Na(+) with the tricationic lanthanide complexes (1-3), [M(PQ)3(DMF)2(H2O)2](3+) (M=Pr(III) (1), Gd(III) (2), and Dy(III) (3); PQ=9,10-phenanthrenequinone), in aqueous solutions. The X-ray diffraction analysis of the modified clays (LCs-C) showed an increase in the interlayer distance (d) as compared to the pure Cloisite Na(+). Field-emission scanning electron microscopy (FE-SEM) was used to study the morphology of the modified clays and the results were demonstrated a homogeneous morphology for the nanohybrids. The thermal behavior of the LCs-C nanohybrids was investigated using thermogravimetric analysis. Solid-state fluorescence properties of the LCs-C nanohybrids were also investigated. The results show that all tricationic complexes have a significant fluorescence at room temperature when the complexes are adsorbed onto Cloisite., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We report the structural and optical properties of Yb(3+), Pr(3+) co-doped Y2O3 nano-phosphor synthesized through solution combustion method. The structural studies reveal the nano-crystalline structure of the sample. The energy dispersive spectroscopy (EDS) measurements confirm the presence of Y, O, Pr and Yb elements in the sample. Fourier transform infrared studies show the vibrational features of the samples. The fluorescence spectra of the samples have been monitored on excitation with 976 nm and the intense green upconversion emission observed at 552 nm is due to (3)P0→(3)H5 electronic transition. The concentration of Pr(3+) ion in the sample is optimized and the fluorescence intensity is maximum at 0.08 mol% of Pr(3+). The power dependence studies reveal the involvement of two photons in the emission process. The possible mechanism of upconversion has been discussed on the basis of schematic energy level diagram. The sample annealed at higher temperature enhances the fluorescence intensity up to 8 times and this enhancement is discussed in terms of the removal of optical quenching centers. The nano-phosphor can be applicable in the field of display devices and green laser., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The coordination structures formed by calcium complexes with nicotinamide (na), isonicotinamide (ina) and picolinamide (pa) and praseodymium bromide-na are reported. The structures of CaCl2·(C6H6N2O)2·2H2O (Ca-na), CaCl2·(C6H6N2O)2·4H2O (Ca-ina), CaCl2·(C6H6N2O)2·5H2O (Ca-pa) and PrBr3·(C6H6N2O)2·6H2O (PrBr-na) in the solid state have been characterized by X-ray single crystal diffraction, FTIR, FIR, THz and Raman spectroscopies. Carbonyl oxygen of nicotinamide is coordinated to Ca(2+), but it is O-monodentate (carbonyl oxygen) and N,O-bidentate ligand (pyridyl nitrogen and carbonyl oxygen) for Pr(3+) to form a chain structure in PrBr-na. For isonicotinamide, only carbonyl oxygen atom is coordinated to Ca(2+). Pyridyl nitrogen and carbonyl oxygen of picolinamide are coordinated to Ca(2+) to form a five-membered ring structure. The crystal structure and spectroscopic results indicate the differences of the coordination of Ca and Pr ions, the changes of hydrogen bonds and conformation of the ligands induced by complexation. Unlike transition metal ions, Sr(2+) or lanthanide ions, Ca(2+) is inclined to coordinate to carbonyl oxygen atoms of the ligands., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Luminescence properties of Pr(3+) activated Sr1.5Ca0.5SiO4 phosphors synthesized by solid state reaction method are reported in this work. Blue, orange red and red emissions were observed in the Pr(3+) doped sample under 444nm excitation and these emissions are assigned as (3)P0→(3)H4, (3)P0→(3)H6 and (3)P0→(3)F4 transitions. The emission intensity shows a maximum corresponding to the 0.5wt% Pr(3+) ion. The decay analysis was done for 0.05 and 0.5wt% Pr(3+) doped samples for the transition (3)P0→(3)H6. The life times of 0.05 and 0.5wt% Pr(3+) doped samples were calculated by fitting to exponential and non-exponential curve respectively, and are found to be 156 and 105μs respectively. The non-exponential behaviour arises due to the statistical distribution of the distances between the ground state Pr(3+) ions and excited state Pr(3+) ions, which cause the inhomogeneous energy transfer rate. The XRD spectrum confirmed the triclinic phase of the prepared phosphors. The compositions of the samples were determined by the energy dispersive X-ray spectra. From the SEM images it is observed that the particles are agglomerated and are irregularly shaped. IR absorption bands were assigned to different vibrational modes. The well resolved peaks shown in the absorption spectra are identical to the excitation spectra of the phosphor samples. Pr(3+) activated Sr1.5Ca0.5SiO4 phosphors can be efficiently excited with 444nm irradiation and emit multicolour visible emissions. From the CIE diagram it can be seen that the prepared phosphor samples give yellowish-green emission., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The interactions of Pr(III) with nucleosides and nucleotides have been studied in different organic solvents employing absorption difference and comparative absorption spectrophotometry. The magnitudes of the variations in both energy and intensity interaction parameters were used to explore the degree of outer and inner sphere co-ordination, incidence of covalency and the extent of metal 4f-orbital involvement in chemical bonding. Various electronic spectral parameters like Slater-Condon (F(k)), Racah (E(k)), Lande parameter (ξ(4f)), Nephelauxatic ratio (β), bonding (b(1/2)), percentage covalency (δ) and intensity parameters like oscillator strength (P) and Judd Ofelt electronic dipole intensity parameter (T(λ), λ=2,4,6) have been evaluated. The variation of these evaluated parameters were employed to interpret the nature of binding of Pr(III) with different ligands i.e. Adenosine/ATP in presence and absence of Ca(2+)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A series of Pr(3+) (1-9 mol%) doped CdSiO(3) nanophosphors have been prepared for the first time by a low temperature solution combustion method using oxalyldihydrizide (ODH) as a fuel. The final product was characterized by Powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The average crystallite size was calculated using Debye-Scherrer's formula and Williamson-Hall (W-H) plots and found to be in the range 31-37 nm. The optical energy band gap (E(g)) of undoped for Pr(3+) doped samples were estimated from Tauc relation which varies from 5.15-5.36 eV. Thermoluminescence (TL) properties of Pr(3+) doped CdSiO(3) nanophosphor has been investigated using γ-irradiation in the dose range 1-6 kGy at a heating rate of 5 °C s(-1). The phosphor shows a well resolved glow peak at ∼171 °C along with shouldered peak at 223 °C in the higher temperature side. It is observed that TL intensity increase with increase of Pr(3+) concentration. Further, the TL intensity at 171 °C is found to be increase linearly with increase in γ-dose which is highly useful in radiation dosimetry. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics was estimated by Luschiks method and the results are discussed., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Spectroscopic investigations on different concentrations (0.1, 0.5, 1.0, 1.5 and 2.0mol%) of Pr(3+) and Nd(3+) doped strontium lithium bismuth borate glasses have been done. X-ray diffraction, SEM with EDS, absorption and luminescence spectra were recorded for all the glass matrices and analyzed. X-ray diffraction profiles and SEM images conformed amorphous nature of investigated glass samples. EDS spectra of host glass and Pr(3+)doped glass matrices gave information about the chemical composition of glass samples. From the absorption spectra of Pr(3+) and Nd(3+) ions, Judd-Ofelt (J-O) intensity parameters (Ω(λ),λ=2, 4 and 6) have been calculated and compared with other glass matrices. The emission characteristics such as radiative lifetimes (τ(R)), measured and calculated branching ratios (β) and stimulated emission cross-sections (σ(P)) have been obtained for the observed emission transitions of Pr(3+) and Nd(3+) ions in the above glass matrix for all the concentrations. From the emission spectra of Pr(3+) and Nd(3+) doped glass matrices, the effect of concentration on the quenching of intensity of (1)D(2)→(3)H(4) transition of Pr(3+) ion and (4)F(3/2)→(4)I(9/2), (4)I(11/2) and (4)I(13/2) transitions of Nd(3+) have been studied and discussed., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The interaction of gly-gly with Pr(III) and Nd(III) have been studied in different aquated organic solvents like CH(3)OH, CH(3)CN, dioxane and DMF by using 4f-4f transitions spectra. Various energy interaction parameters like Slater Condon (F(k)), Racah (E(k)), Lande (ξ(4f)), nephelauxetic effect (β), bonding (b(1/2)) and percent covalency (δ) parameters have been calculated to explain the nature of complexation. The intensity parameters like oscillator strength (P) and Judd-Ofelt parameters (T(λ), λ=2, 4, 6) also support the mode of binding of gly-gly to metal ions. The results show that Pr(III) and Nd(III) with gly-gly form complexes by ionic linkages with carboxylate anion with weak covalency. The protonation constants and metal-ligand stability constants have also been determined by potentiometric measurements in aqueous medium at different temperatures (290, 300 and 310 K) at constant ionic strength, 0.1 mol dm(-1). The results show the formation of metal-ligand complexes in the stoichiometric ratio 1:1. The stability of complexes is more in Nd(III) complexes as compared to Pr(III) complexes. Thermodynamic parameters (ΔG, ΔH and ΔS) of complexes were also calculated and the negative values of ΔG and ΔH show that the complex reactions are spontaneous and exothermic. The positive values of ΔS indicate high stability of complex reactions which are enthalpy-driven., (Copyright © 2012 Elsevier B.V. All rights reserved.)

We report on the spectroscopic properties of Pr(3+)-doped boro-phosphate, boro-germo-silicate and tellurite glasses. The stimulated absorption and emission cross sections were estimated. Only one emission at 596 nm and 605 nm is observed in Pr(3+)-doped boro-phosphate and boro-germo-silicate glasses, respectively, while three emissions at 605 nm, 612 nm and 645 nm are observed in Pr(3+)-doped tellurite glass when excited at 467 nm. The fluorescence lifetime at 600 nm in Pr(3+)-doped boro-phosphate, boro-germo-silicate and tellurite glasses is 137 μs, 73 μs and 51 μs, respectively. The emissions from Pr(3+)-doped boro-phosphate, boro-germo-silicate and tellurite glasses show different decay behaviors and can be well explained by multiphonon relaxation theory., (Copyright © 2012 Elsevier B.V. All rights reserved.)

An investigation on the absorption spectra of the praseodymium chloride (PrCl(3)) in methanol, iso-propanol and butanol is carried out between 190 nm and 1100 nm. We have observed and assigned six energy bands of the 4f(2) electronic configuration of the Pr(3+) ion in the visible to near-infra-red and one due to 4f5d configuration in the ultraviolet region. The 4f5d band has been detected properly for low concentration of PrCl(3). We have also constructed a free-ion Hamiltonian and calculated the energy levels of the 4f(2) configuration theoretically. Hence, the best fit free-ion parameters are deduced., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The complexation of thiosemicarbazide with Pr(III) and Nd(III) in absence and presence of Zn(II), a soft metal ion in aqueous and organic solvents like CH(3)OH,CH(3)CN, dioxane (C(4)H(8)O(2)) and DMF (C(3)H(7)NO) and their equimolar mixtures are discussed by employing absorption difference and comparative absorption spectrophotometry. Complexation of thiosemicarbazide with Pr(III) and Nd(III) is indicated by the changes in the absorption intensity following the subsequent changes in the oscillator strength of different 4f-4f bands and Judd-Ofelt intensity (T(λ)) parameters. The other spectral parameters like energy interaction parameters namely Slater-Condon (F(k)), Racah (E(k)), Lande (ξ(4f)), Nephelauxetic ratio (β) and bonding parameters (b(1/2)) are further computed to explain the nature of complexation. The difference in the energy parameters with respect to donor atoms and solvents reveal that the chemical environment around the lanthanide ions has great impact on f-f transition and any change in the environment result in modification of the spectra. Various solvents and their equimolar mixtures are also used to discuss the participation of solvents in the complexation., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The binding of neodymium(III) and praseodymium(III) complexes containing 1,10-phenanthroline, [M(phen)2Cl3·OH2] (M=Nd (1), Pr (2)), to DNA has been investigated by absorption, emission, and viscosity measurements. The complexes show absorption decreasing in charge transfer band, fluorescence decrement when bound to DNA. The binding constant Kb has been determined by absorption measurement for both complexes and found to be (6.76±0.12)×10(4) for 1 and (1.83±0.15)×10(4)M(-1), for 2. The fluorescence of [M(phen)2Cl3·OH2] (M=Nd (1), Pr (2)) has been studied in detail. The results of fluorescence titration reveal that DNA has the strong ability to quenching the intrinsic fluorescence of Nd(III) and Pr(III) complexes through the static quenching procedure. The binding site number n, apparent binding constant Kb and the Stern-Volmer constant kSV are determined. Thermodynamic parameters, enthalpy change (ΔH°) and entropy change (ΔS°), are calculated according to relevant fluorescent data and Van't Hoff equation. The experimental data suggest that the complexes bind to DNA by non-intercalative mode. Major groove binding is the preferred mode of interaction for [M(phen)2Cl3·OH2] (M=Nd (1), Pr (2)) with DNA., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Liposomes are ideal dermal drug delivery systems because of their ability to alter the biodistribution profile of incorporated drugs. In a novel approach to optimize the liposomal microstructure, lysine derivatives were employed. The effect of the oligopeptides Lys-5 and Lys-7 on the structure as well as on the skin permeation of the antimycotic drug fluconazole in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine vesicles was studied using a variety of techniques. It was demonstrated by addition of the shift reagent praseodymium(III)chloride and subsequent (31)P NMR measurements that the liposomes produced consisted mainly of unilamellar vesicles. This was confirmed by cryo-transmission electron microscopy. The addition of Lys-5 and Lys-7 induced a structural change resulting in a decrease in particle size between 10% and 40% and a retarding effect on fluconazole skin permeation., (Copyright © 2011 Wiley-Liss, Inc. and the American Pharmacists Association)

Frequency upconversion in triply ionized praseodymium doped glass with composition TeO(2)-Na(2)O (TNO) system under the excitation with a laser light from a dye laser has been reported and the covalency, bonding parameter, nephalauxetic effect which provides the information about the nature of bonding between the lanthanide ions and the surrounding oxygens for the present glassy material calculated. The energy transfer route followed by the two excited praseodymium ions is observed to be the leading process for the upconversion emission., (Copyright 2010. Published by Elsevier B.V.)

Studying the absorption difference and comparative absorption spectra of the interaction of Pr(III) and Nd(III) with l-phenylalanine, l-glycine, l-alanine and l-aspartic acid in the presence and absence of Ca(2+) in organic solvents, various energy interaction parameters like Slater-Condon (F(K)), Racah (E(k)), Lande factor (xi(4f)), nephelauxetic ratio (beta), bonding (b(1/2)), percentage-covalency (delta) have been evaluated applying partial and multiple regression analysis. The values of oscillator strength (P) and Judd-Ofelt electric dipole intensity parameter T(lambda) (lambda = 2, 4, 6) for different 4f-4f transitions have been computed. On analysis of the variation of the various energy interaction parameters as well as the changes in the oscillator strength (P) and T(lambda) values reveal the mode of binding with different ligands.

In this paper, we describe the structural and sensing properties of high-k PrY(x)O(y) sensing films deposited on Si substrates through reactive co-sputtering. Secondary ion mass spectrometry and atomic force microscopy were employed to analyze the compositional and morphological features of these films after annealing at various temperatures. The electrolyte-insulator-semiconductor (EIS) device incorporating a PrY(x)O(y) sensing membrane that had been annealed at 800 degrees C exhibited good sensing characteristics, including a high sensitivity (59.07 mV pH(-1) in solutions from pH 2 to 12), a low hysteresis voltage (2.4 mV in the pH loop 7-->4-->7-->10-->7), and a small drift rate (0.62 mV h(-1) in the buffer solution at pH 7). The PrY(x)O(y) EIS device also showed a high selective response towards H(+). This improvement can be attributed to the small number of crystal defects and the large surface roughness. In addition, the enzymatic EIS-based urea biosensor incorporating a high-k PrY(x)O(y) sensing film annealed at 800 degrees C allowed the potentiometric analysis of urea, at concentrations ranging from 1 to 16 mM, with a sensitivity of 9.59 mV mM(-1).

Energy transfer excited upconversion emission in Nd3+/Pr3+-codped tellurite glass have been studied on pumping with 800 nm wavelength. The upconversion emission bands from Pr3+ ion are observed at the 488, 524, 546, 612, 647, 672, 708 and 723 nm due to the (3P0 + 3P1)-->3H4, 3P1-->3H5, 3P0-->3H5, 3P0-->3H6, 3P0-->3F2, 3P1-->3F3, 3P0-->3F3 and 3P0-->3F4 transitions, respectively. The addition of ytterbium ions (Yb3+) on the upconversion emission intensity is also studied and result shows an eight times enhancement in the upconversion intensity at 488 nm from Pr3+ ions. The pump power and concentration dependence studies are also made. It is found that Yb3+ ions transfer its excitation energy to Nd3+ from which it goes to Pr3+. No direct transfer to Pr3+ is seen. This is verified by codoping Nd3+ and Pr3+ into the host.

Using the decay curve analysis frequency upconversion under continuous wave NIR laser radiation ( approximately 890 nm) following the non-resonant excitation at higher energies than 1G4 level has been reported. The decay curve of the antistokes emission (3P0-->3H4) shows similar behavior as that of the stokes emission (3P0-->3H4) and does not show any rise time attributing to the excited state antistokes absorption assisted by phonon emission. The covalency, bonding parameters and nephalauxetic effect for the present system has also been determined.

Photocatalytic degradation of phenol in water was examined using Pr-doped TiO(2) nanoparticles. These photocatalysts were synthesized by an acid-peptized sol-gel method from titanium tetra-isopropoxide with different concentrations of Pr(III) dopant and calcination temperatures. Several tools such as XRD, BET surface area, SEM, and EDX, were used to evaluate particle structure, size distribution, and composition. The optical absorption properties of the prepared particles were also measured. Photocatalytic activity of the particles was studied in a batch reactor containing phenol solution with 400W UV irradiation. Parameters affecting photocatalytic process such as the catalyst crystallinity, light absorption efficiency, the dosage of catalyst, dopant and phenol concentrations were investigated. The Pr-doped TiO(2) showed high activity for photocatalytic degradation of phenol. The presence of Pr ions in the TiO(2) particles would cause a significant absorption shift towards the visible region. The degradation process was optimized using 1g/L Pr-doped TiO(2) with a Pr(III) concentration of 0.072 mol% after 2h irradiation. It was shown that photodegradation followed a pseudo-first-order kinetics and the rate constant changed with phenol concentration.

The optical absorption spectra of [Pr(acac)(3)(H(2)O)(2)].H(2)O, [Pr(acac)(3)phen.H(2)O] and [Pr(acac)(3)bpy] (where acac is the anion of acetylacetone, phen is 1,10-phenanthroline and bpy is 2,2'-bipyridyl) have been analyzed in the visible region in a series of non-aqueous solvents (methanol, ethanol, isopropanol, chloroform, acetonitrile and pyridine). The complexes display four non-hypersensitive 4f-4f transitions ((3)P(2), (3)P(1)+(1)I(6), (3)P(0) and (1)D(2)) from the (3)H(4) ground state. The band shape of the transitions shows remarkable changes upon dissolving in different solvents. Distinctively different band shapes have been observed for phen and bpy complexes. The phen is more effective in producing changes and the splitting of the bands is more pronounced in phen complex since it is a stronger ligand and leads to stronger Pr-N(phen) bond. The splitting of the bands is indicative of partaking of f-orbitals in bonding. The NMR signals of heterocyclic amines have been shifted to high fields while the resonances due to acetylacetone moiety have moved to low fields which is the consequence of change in geometry of the complexes upon coordination of the heterocyclic amines and reflects the importance of geometric factor (3cos(2)theta-1) in changing sign of the shift and to a good approximation the shifts arise predominantly from the dipolar mechanism. The phen complexes have narrower line width than bpy complexes. The line broadening in the case of bpy complexes is suggestive of exchange between inter-converting forms. The bpy possesses some degree of rotational freedom about C(6)-C(6') bond and the two pyridine rings undergo scissoring motion with respect to each other.

The use of TVEX-PHOR resin for the sorption of praseodymium (III), holmium (III) and cobalt (II) from nitrate medium was carried out using batch and column techniques. Various parameters affecting the uptake of these metal ions such as v/m ratio, pH and the metal ion concentration were separately studied. Effect of temperature on the equilibrium distribution values has been studied to evaluate the changes in standard thermodynamic quantities. Experimental results of the investigated metal ions were found to fit to Freundlich isotherm model over the entire studied concentration range. Selectivity sequence of the resin for these metals is Ho>Pr>Co. The recovery of the investigated metals from the loaded resin is preformed with 0.1M sulphuric acid.

A series of luminescent praseodymium complexes with different aromatic carboxylic acids have been synthesized and characterized. The photophysical properties of these complexes have been studied with ultraviolet spectra, phosphorescence spectra and fluorescence spectra. Ultraviolet absorption spectra show that the praseodymium complexes systems with aromatic carboxylate form the more extensive conjugated systems to be suitable for the distribution of electron in the whole coordination environment, resulting in the energy decrease and red-shifts of ultraviolet spectral bands. Phosphorescence spectra suggest that excited triplet state of aromatic carboxylic acids, which can indicate the energy match and intermolecular energy transfer process between the excited triplet state of ligands and the resonant emissive energy level of Pr ions. The emission spectra of all praseodymium complexes show two emission peaks under the excitation band of 245 nm at about 395 and 595 nm, respectively, while one peak at about 595 nm under 415 nm excitation, which attributed to be 1S0-->1I6 (395 nm) transition and the characteristic emission 1D2-->3H4 (595 nm) transition of Pr3+ ion. The 1S0-->1I6 transition can be speculated to belong to the transition of charge transfer state, and the 1D2-->3H4 can be further proved that there exists an antenna effect in the luminescence of praseodymium with aromatic carboxylic acids. In conclusion, the praseodymium complexes systems can realize the double proton light conversion both in the ultraviolet and visible region, which can be further studied to have potential application.

Comparative absorption and spectral analysis of 4f-4f transitions of Pr(III) and glutathione reduced (GSH) complex in presence and absence of Zn(II) is carried out in different aquated organic solvents of CH3OH, CH3CN, DMF and dioxane and their equimolar mixtures at different pH (3.0, 4.0, 5.0 and 6.0). The values of experimentally calculated oscillator strengths (P) and computed values of Judd-Ofelt electric dipole intensity parameters, Tlambda (lambda=2, 4, 6) are discussed for different 4f-4f transitions in different experimental conditions. The changes in the values of oscillator strengths (P) and Tlambda parameters suggest the specific correlation between relative intensities, ligand structures and nature of interaction of Pr(III) with GSH in the presence and absence of Zn(II).

Infrared and Raman spectra of four rare earth (Ho, Eu, Nd and Pr) double sulphates have been recorded and analysed based on the vibrations of methyl ammonium cations, sulphate anions and water molecules. Formation of hydrogen bonds of the type N-H...O and O-H...O are identified in all the compounds. Bifurcated hydrogen bonds are present in the compounds with dimethyl ammonium cations. The sulphate anions are distorted and occupy a lower site symmetry in the compounds. The bands obtained for (CH(3))(2)NH(2) and SO(4)(2-) ions indicate that the structural bonding of (CH(3))(2)NH(2)Eu(SO(4))(2).H(2)O and (CH(3))(2)NH(2)Ho(SO(4))(2).4H(2)O is identical. Electronic transition bands of Eu(3+) and Nd(3+) observed in the Raman spectra of these two compounds have been identified and discussed.

A series of new coordination complexes of La(III) and Pr(III) with hydrazones, derived from 1,1-diacetylferrocene and different aromatic acid hydrazides have been synthesized and characterized by elemental analyses, electrical conductance, magnetic moment, IR, (1)H NMR, UV-vis spectra and molar conductance. The thermal behaviour of the complexes under non-isothermal condition was investigated by TG and DTG techniques. The antifungal activity of hydrazones and their corresponding complexes were also investigated.

Lanthanum(III) and praseodymium(III) complexes with dithiocarbamates have been synthesized by the reactions of lanthanum(III) and praseodymium(III) chloride with barium dithiocarbamate and complexes of type [LnCl(L)H2O]n have been obtained (where Ln=La(III) or Pr(III); L=barium salt of dithiocarbamate derived from glycine, L-leucine, L-valine, DL-alanine). The complexes have been characterized by elemental analysis, molar conductance, electronic absorption and fluorescence, infrared, far infrared, 1H NMR spectral studies. The presence of coordinated water molecule is inferred from thermogravimetric analysis which indicates the loss of one water molecule at 150-170 degrees C. The oscillator strength, Judd-Ofelt intensity parameter, stimulated emission cross-section, etc. have been obtained for different transitions of Pr3+.

A single-crystal of PrCl3.D-ribose.5H2O was obtained from a methanol-water solution and its structure determined by X-ray crystallography. Two configurations of the complex, as a pair of isomers, were found in the single-crystal in a disordered state, which differs from that reported previously. The ligand of one of the complexes is alpha-D-ribopyranose in the 4C1 conformation, and the ligand of the other is beta-D-ribopyranose in the 1C4 conformation. The alpha:beta anomeric ratio is 54:46. Both ligands of the two isomers provide three hydroxyl groups in an axial-equatorial-axial orientation for coordination. The Pr3+ ion is nine-coordinated, with five Pr-O bonds from water molecules, three Pr-O bonds from the hydroxyl groups of the D-ribopyranose and one Pr-Cl bond from chloride ion. The hydroxyl groups, water molecules, and chloride ions form an extensive hydrogen-bond network. The IR spectral C-C, O-H, C-O, and C-O-H vibrations are shifted in the complex, compared to those in d-ribose, and the IR results are in accord with those obtained from the X-ray diffraction study.

The absorption and the fluorescence spectra of Pr3+ ion doped in aluminum, barium, calcium fluoride (ABCF) glass have been studied. Judd-Ofelt theory has been used to derive the optical parameters, viz. the oscillator strength, transition probability, branching ratio, stimulated emission cross section, etc. A broadband upconversion has been observed at different wavelengths throughout the visible region when pumped with 810 nm radiation from a Ti-sapphire laser.

Pr(III) and Nd(III) are hard acceptors in HSAB (hard and soft acid base) sense and hence are known to exhibit practically a little affinity towards electrons. At the same time these metal ions show strong preference for oxygen donor chelating ligands. The ligands chosen for this study are structurally related diols, viz. butane-1,4, butene-1,4 and butyne-1,4-diols which form identical seven membered chelate ring by coordinating to metals in a bidentate manner through oxygen on 1 and 4 positions of the diol molecules. Complexation of these diols with Pr(III) and Nd(III) was carried out in DMF, CH3OH, CH3CN and their equimolar binary mixtures using comparative absorption spectrophotometry of 4f-4f transitions. The variation of oscillator strengths (P) of different 4f-4f bands as well as the magnitude and variation of Judd-Ofelt electric dipole intensity parameters (T lambda, lambda = 2, 4, 6) was discussed. They correlate the interaction between the metal 4f-orbitals of Pr(III) and Nd(III) with the pi-electron densities of the double and triple bonds present in butene-1,4 and butyne-1,4-diols, respectively. The value of empirical intensity parameter [T lambda(complex)/T lambda (aquo)] was calculated and its plot against oscillator strength (P) is drawn.

The absorption and fluorescence spectra of Pr(3+) doped in tellurite glass has been recorded and analyzed in terms of Judd-Ofelt theory. The lifetime of (3)P(0) and (3)P(1) levels has been measured. Fluorescence quenching has been observed for higher concentrations of Pr(3+) ion. The temperature dependence of the fluorescence intensity and the lifetime of the (3)P(0) level has been investigated and found that they decrease with the increase of the temperature.

Ten new lanthanum(III) and praseodymium(III) complexes of the general formula Na[La(L)2H2O] (Ln=La(III) or Pr(III); LH2=thiosemicarbazones) derived from the condensation of isatin with 4-phenyl thiosemicarbazide, 4-(4-chlorophenyl) thiosemicarbazide, 4-(2-nitrophenyl) thiosemicarbazide, 4-(2-bromophenyl) thiosemicarbazide and 4-(2-methylphenyl) thiosemicarbazide, have been synthesized in methanol in presence of sodium hydroxide. The XRD spectra of the complexes were monitored to verify complex formation. The complexes have also been characterized by elemental analysis, molar conductance, electronic absorption and fluorescence, infrared, far infrared, 1H and 13C NMR spectral studies. Thermal studies of these complexes have been carried out in the temperature range 25-800 degrees C using TG, DTG and DTA techniques. All these complexes decompose gradually with the formation of Ln2O3 as the end product. The Judd-ofelt intensity parameter, oscillator strength, transition probability, stimulated emission cross section for different transitions of Pr3+ for 4-phenyl thiosemicarbazones have been calculated.

The coordination chemistry of glutathione reduced (GSH) is of great importance as it acts as excellent model system for the binding of metal ions. The GSH complexation with metal ions is involved in the toxicology of different metal ions. Its coordination behaviour for soft metal ions and hard metal ions is found different because of the structure of GSH and its different potential binding sites. In our work we have studied two chemically dissimilar metal ions viz. Pr(III), which prefer hard donor site like carboxylic groups and Zn(II) the soft metal ion which prefer peptide-NH and sulphydryl groups. The absorption difference and comparative absorption spectroscopy involving 4f-4f transitions of the heterobimetallic Complexation of GSH with Pr(III) and Zn(II) has been explored in aqueous and aquated organic solvents. The variation in the energy parameters like Slater-Condon (F(K)), Racah (E(K)) and Lande (xi(4f)), Nephelauxetic parameter (beta) and bonding parameter (b(1/2)) are computed to explain the nature of complexation.

The extraction behaviour of Pr(III) from aqueous nitric acid medium employing benzoylacetone has been studied in presence of two crown ethers, viz., 15-crown-5 and benzo-15-crown-5 in chloroform medium using UV-vis absorption spectroscopy. The binary equilibrium constant (logk(ex)) for the complex [Pr(benzoylacetonate)(NO3(-))2(H(2)O)] in organic phase was found to be 1.170. The overall equilibrium constants (logK) for the ternary species [Pr(benzoylacetonate)(crown ether)(NO3(-))(2)] were estimated to be 4.01 and 4.41 for 15-crown-5 and benzo-15-crown-5, respectively. The trend in the equilibrium constant values were very much in accordance with the nature of substitution of the donor moiety. The extraction of Pr(III) by the benzoylacetone-crown ether combination was maximum at pH 3.0 and extraction decreases with increase in pH. It has been found that the extent of extraction of Pr(III) in organic phase as the binary as well as ternary complex [Pr(benzoylacetonate)(NO3(-))(2)(H(2)O)] and [Pr(benzoylacetonate)(crown ether)(NO3(-))(2)] increases with increase in concentration of the ligand. Similar trend is observed in the extraction by only donors. Enthalpies and entropies of formation for the ternary extraction process have been estimated. In addition, the effect of NaNO(3) as foreign salt was also studied and it was observed that with increase in ionic strength, percentage extraction increases.

The kinetics of complexation of Zn(II) with Pr2(GSH)2.(H2O)4 1 (GSH-glutathione) to form Pr2(GSH)2Zn(H2O)6 complex 2 has been investigated at 30 degrees C by following the changes in the intensity (absorbance, molar absorptivity) and intensity (oscillator strength P and Judd-Ofelt-T(lambda) intensity) parameters in equimolar DMF-Water. In order to support kinetics data, the complex 1 and 2 have been synthesized and characterized by elemental analysis, IR and 1H NMR spectral analysis. Molecular weights of 1 and 2 determined by ebullioscopic and cryoscopic methods and preliminary molecular modeling experiments have helped in proposing most probable structures for 1 and 2. Kinetics showed first order dependence, in terms of concentration of Zn(II) and complex 1, on the rate of formation of complex 2. Generally, hypersensitive transitions (the transitions obeying /DeltaJ/ selection rules) were used in spectra-structure correlation studies. We have used the four 4f-4f transitions of Pr(III), which do not obey selection rules, yet are substantially sensitive to coordination changes, for kinetic study. The rate constants evaluated from individual 4f-4f bands are quite close hence supporting our observations on ligand mediated pseudohypersensitivity.

Rare earth doped oxyfluoroborate glasses have been prepared with different concentration of Eu3+. The UV-Vis/NIR optical absorption, laser induced fluorescence and photoacoustic spectra of Eu3+ in this host have been studied. Different optical parameters such as oscillator strength, Judd-Ofelt intensity parameter, stimulated emission cross-section, transition probability, branching ratio and radiative lifetime, etc. have been calculated. Lifetime of the 5D0 level at various concentrations of Eu3+ have been used to explain the concentration dependent fluorescence quenching. The mechanism of quenching was found to be dipole-dipole. Energy transfer have also been studied from Eu3+ to Pr3+ in sample with 1 mol% (Eu3+) + 1 mol% Pr3+.

Absorption spectroscopic studies on the mixed-ligand complexes of Pr (III) and Nd (III) with 2,2'-bipyridyl and thiocyanate in pyridine, DMSO, DMF and methanol are presented. The oscillator strengths for the hypersensitive and non-hypersensitive transitions have been calculated and variation in the oscillator strength and band shapes with respect to solvent type is rationalized in terms of solvent structures and coordinating properties. A comparison is made with 1,10-phenanthroline complexes and has been shown that bpy is a weaker ligand than phen for these ions. Pyridine has been found most effective in promoting 4f-4f intensity and the increase in the oscillator strength in this solvent is due to dynamic ligand polarization mechanism., (Copyright 2002 Elsevier Science B.V.)

The absorption und magnetic circular dichroism spectra of the dissolved trigonal-bipyramidal complex Pr[N(SiMe3)2]3(CNtBu)2 (1) as well as the luminescence and absorption spectra of both solid 1 and solid Pr[N(SiMe3)2]3(CNC6H11)2 (2) (pellets, unoriented single crystals) were measured at ambient and low temperatures. Because of the violation of the selection rules for D3h symmetry by both compounds a reliable crystal field(CF) splitting pattern for the ground manifold 3H4, but only a plausible for the f 2 configuration could be derived on the basis of these measurements. The latter could be simulated with a reduced r.m.s. deviation of 32.6 cm(-1) for 29 assignments by fitting the free parameters of a phenomenological Hamiltonian. The adequacy of the calculated wavefunctions of this fit in the low energy range is proved by the excellent agreement of calculated and experimental temperature dependence of mu2(eff) for compound 1. The CF parameters of this fit are considered as a "master set" of CF parameters for future CF analyses of the electronic structures of trigonal bipyramidally coordinated lanthanide(III) systems.

The crystal structure of praseodymium chloride.alpha-D-ribopyranose pentahydrate, PrCl3-C5H10O5-5 H2O, M(r)=487.47, a=9.1989(8), b=8.8214(7), c=9.8233(9) A, beta=94.060(3) degrees, V=795.2(1) A(3), Z=2, mu=0.71073 A and R=0.0418 for 1923 observed reflections and 172 parameters has been determined. The sugar provides three hydroxyl groups, ax-eq-ax for coordination. The Pr(3+) ion is nine-coordinated with five Pr-O bonds from water molecules, three from hydroxyl groups and one from chloride. The OH, CO stretching vibrations and COH bending vibrations are shifted in the complex IR spectrum and the hydroxyl groups, water molecules, chloride ions form an extensive hydrogen-bond network.

The crystal structure of 2NdCl3.galactitol.14H2O has been determined. The crystal system is triclinic, space group: -1, with unit-cell dimensions: a = 9.736(2), b = 10.396, c = 8.027 A; alpha = 108.05(3), beta = 92.68(3), gamma = 88.44(3) degrees, V= 771.6(3) A3, Z = 2. Each Nd atom is coordinated to nine oxygen atoms, three from the alditol and six from water molecules, with Nd-O distances from 2.461 to 2.552 A. The seventh water molecule is hydrogen-bonded by the hydroxyl hydrogen on O-1 (O-1-H-ll...O-10, 2.639 A). The FT-IR spectra of 2NdCl3.galactitol.14H2O and 2PrCl3.galactitol.14H2O are analogous, and show that Pr and Nd have the same coordination mode. The IR results are consistent with the crystal structures.

The title compound, PrCl3.C6H12O6.9 H2O crystallized in the monoclinic space group P2(1)/n with cell dimensions a = 15.8293(3), b = 8.67750(10), c = 16.2292(3) A, beta = 107.0788(8) degrees, V = 2130.92(6) A3 and Z = 4. Each Pr ion is coordinated to nine oxygen atoms, two from the inositol and seven from water molecules, with Pr-O distances from 2.4729 to 2.6899 A; the other two water molecules are hydrogen-bonded. No direct contacts exist between Pr and Cl. There is an extensive network of hydrogen bonds formed by hydroxyl groups, water molecules, and chloride ions. The IR spectra of Pr-, Nd-, and Sm-inositol complexes are similar, which shows that the three metal ions have the same coordination mode. The IR results are consistent with the crystal structure.

Tb3+-doped oxyfluoroborate glasses have been prepared for different concentrations of Tb. The absorption, fluorescence and photoacoustic spectra of these have been recorded and studied. It is marked that the fluorescence intensity of different fluorescence transitions decreases with the increase of Tb ion concentration in the glass. This quenching at higher concentration is due to the energy transfer among the excited and nearest neighbor unexcited Tb ions in the glass. The lifetime measurement confirms it, as the lifetime of a particular state was found to decrease with the increase of Tb ion concentration in the glass. The mechanism of the energy transfer process was determined to involve quadrupole quadrupole interaction. We have also studied the energy transfer from Tb3+-->Pr3+ when both the rare earths are doped together in the glass. A decrease in the lifetime of the 5D4 level of Tb3+ with the increase of Pr3+ concentration confirms this.

A number of complexes are synthesised with Pr(III) and Nd(III) employing the mono- and disaccharides, D-glucose, D-galactose, D-mannose, D-arabinose, D-ribose, D-xylose, maltose and lactose. The complexes are characterised by various spectral and analytical techniques, and based on these data, appropriate structures were assigned for all complexes.