Migration of Trivalent Praseodymium from Tombarthite Sewage by Microtubule Ultrafiltration Reactor with Organophosphorus in Fuel Oil.

A microtubule ultrafiltration reactor (MUFR), with an organophosphorus system containing a sewage section with buffer liquid acetic acid and an enrichment section with aqua fortis liquid and organophosphorus dissolved in fuel oil, has been studied for praseodymium(III) migration. Many factors of praseodymium(III) migration using MUFR need to be explored, including hydrogen ion molarity (or pH), cinit of praseodymium(III), the different ionic strengths of rare-earth mine sewage, the volume ratio of organophosphorus fuel oil and aqua fortis liquid (O/A), aqua fortis' molarity, organophosphorus' molarity, and the effects of different acid liquids in the enrichment section on praseodymium(III) migration with MUFR. The virtues of MUFR compared to conventional migration were explored. The effects of the hydrodynamic properties (stability and flow velocity) and UF system parameters (internal diameter of the microtubule, tubule shell thickness, void ratio), etc., on the mass migration performance of the MUFR process for praseodymium(III) migration were also studied. The experimental results show that the best migration prerequisites of praseodymium(III) were obtained as follows: an aqua fortis molarity of 4.00 mol/L, an organophosphorus molarity of 0.200 mol/L, an O/A of 0.6 in the enrichment section, and a pH value of 4.80 in the sewage section. The ionic strength of rare-earth mine sewage had no obvious effect on praseodymium(III) migration. When the cinit of praseodymium(III) molarity was 1.58 × 10-4 mol/L, the migration percentage of praseodymium(III) reached 95.2% in 160 min.

Two new lanthanide complexes with 5-(Pyrazol-1-yl)nicotinic acid: Structures and their anti-cancer properties.

Two new lanthanide complexes [PrL2(EA)2]NO3 (complex 1) and [SmL2(EA)2]NO3 (complex 2) (H2L = 5-(Pyrazol-1-yl)nicotinic acid, EA = CH3CH2OH) 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.

Nanotized praseodymium oxide collagen 3-D pro-vasculogenic biomatrix for soft tissue engineering.

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.

Synthesis of Nano-Praseodymium Oxide for Cataluminescence Sensing of Acetophenone in Exhaled Breath.

In this work, we successfully developed a novel and sensitive gas sensor for the determination of trace acetophenone based on its cataluminescence (CTL) emission on the surface of nano-praseodymium oxide (nano-Pr6O11). The effects of working conditions such as temperature, flow rate, and detecting wavelength on the CTL sensing were investigated in detail. Under the optimized conditions, the sensor exhibited linear response to the acetophenone in the range of 15-280 mg/m3 (2.8-52 ppm), with a correlation coefficient (R2) of 0.9968 and a limit of detection (S/N = 3) of 4 mg/m3 (0.7 ppm). The selectivity of the sensor was also investigated, no or weak response to other compounds, such as alcohols (methanol, ethanol, n-propanol, iso-propanol, n-butanol), aldehyde (formaldehyde and acetaldehyde), benzenes (toluene, o-xylene, m-xylene, p-xylene), n-pentane, ethyl acetate, ammonia, carbon monoxide, carbon dioxide. Finally, the present sensor was applied to the determination of acetophenone in human exhaled breath samples. The results showed that the sensor has promising application in clinical breath analysis.

Toxicity response of highly colloidal, bioactive, monodisperse SiO2@ Pr(OH)3 hollow microspheres.

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), N2-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 Pr3+ 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 Pr3+ 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.

Photo-assisted SCR removal of NO by upconversion CeO2/Pr3+/attapulgite nanocatalyst.

The emission of nitrogen oxides has caused severe harm to the ecosystem; thus, the development of low-cost and high-efficiency denitrification catalysts and new methods are of great significance. In this work, a co-precipitation method was employed to prepare Pr-doped CeO2/attapulgite (CeO2/Pr3+/ATP) nanocomposites. X-ray diffraction (XRD), photoluminance spectroscopy (PL), ultraviolet-visible diffuse reflectance (UV-Vis), Fourier transform infrared (FT-IR), and high-resolution transmission electron microscopy (HRTEM) were utilized to characterize the products. Results showed that the CeO2/Pr3+ nanoparticles were uniformly coated on the surface of ATP and demonstrated outstanding upconversion effect which converted the visible light to ultraviolet light. The upconversion luminescence of CeO2/Pr3+/ATP was strongest when the molar doping amount of Pr was 1 mol%, and the photo-SCR denitrification achieved the highest of 90% conversion and 95% selectivity when the loading amount of CeO2/Pr3+ was 40 wt%. The ATP and CeO2/Pr3+ constructed an indirect Z-type heterojunction structure mediated by oxygen vacancy which benefited the separation of charge carriers and enhanced the reduction-oxidation potentials, both are responsible for the remarkable denitrification performance.

A novel optical approach for determination of prolactin based on Pr-MOF nanofibers.

The analytical quantification and follow-up of the hormone prolactin is very important in clinical diagnosis (e.g., in cases of breast cancer), treatment, and the medical laboratory. The development of a new simple, fast, and less costly method is of considerable importance. Novel praseodymium metal-organic framework nanofibers (Pr-MOF-NFs) were synthesized by a facile and simple method for the determination of human prolactin in serum samples. The Pr-MOF-NFs were well characterized with several spectroscopic tools, such as mass spectrometry, Fourier transform IR spectroscopy, UV-vis spectroscopy, elemental analysis, X-ray diffraction, field-emission scanning electron microscopy combined with energy-dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy. The photoluminescence of Pr-MOF-NFs was investigated, and the results revealed that Pr-MOF-NFs could be used as a sensitive and selective nanofiber optical sensor for the detection of human prolactin. The calibration graph was studied over a wide prolactin concentration range of 0-200 ng/mL, with limits of detection and quantitation of 0.276 and 0.838 ng/mL, respectively, lower than the values mentioned in previous reports. The correlation coefficient was 0.9792. Moreover, the Pr-MOF-NFs were applied successfully for the detection of serum human prolactin at clinically applicable concentrations without interference from several types of hormones and various interfering analytes. Graphical abstract.

Dual-photosensitizer coupled nanoscintillator capable of producing type I and type II ROS for next generation photodynamic therapy.

The current photodynamic therapy (PDT) is majorly hindered by the shallow penetration depth and oxygen dependency, limiting its application to deep-seated solid hypoxic tumors. Thus, it is meaningful to develop efficient X-ray mediated PDT system capable of generating reactive oxygen species (ROS) under both the normoxic and hypoxic conditions. Herein, we report the synthesis and characterization of nanocomposite, YAG:Pr@ZnO@PpIX with an amalgamation of UV-emitting Y2.99Pr0.01Al5O12 (YAG:Pr) nanoscintillator, and zinc oxide (ZnO) and protoporphyrin IX (PpIX) as photosensitizers. YAG:Pr surface was coated with a ZnO layer (∼10 nm) by atomic layer deposition, and then PpIX was covalently conjugated via a linker to give YAG:Pr@ZnO@PpIX. The photo- and cathodoluminescence analyses gave the evidences of efficient energy transfer from YAG:Pr to ZnO at ∼320 nm, and YAG:Pr@ZnO to PpIX at Soret region (350-450 nm). The nanohybrid was able to produce both, Type I and Type II ROS upon direct and indirect photoactivation with UV365nm and UV290nm, respectively. In vitro cytotoxicity of non-activated YAG:Pr@ZnO@PpIX in mouse melanoma cells revealed low toxicity, which significantly enhanced upon photoactivation with UV365nm indicating the photokilling property of the nanohybrid. Overall, our preliminary studies successfully demonstrate the potential of YAG:Pr@ZnO@PpIX to overcome the limited penetration and oxygen-dependency of traditional PDT.

Effects of acidic peptide size and sequence on trivalent praseodymium adduction and electron transfer dissociation mass spectrometry.

Using the lanthanide ion praseodymium, Pr(III), metallated ion formation and electron transfer dissociation (ETD) were studied for 25 biological and model acidic peptides. For chain lengths of seven or more residues, even highly acidic peptides that can be difficult to protonate by electrospray ionization will metallate and undergo abundant ETD fragmentation. Peptides composed of predominantly acidic residues form only the deprotonated ion, [M + Pr - H]2+ ; this ion yields near complete ETD sequence coverage for larger peptides. Peptides with a mixture of acidic and neutral residues generate [M + Pr]3+ , which cleaves between every residue for many peptides. Acidic peptides that contain at least one residue with a basic side chain also produce the protonated ion, [M + Pr + H]4+ ; this ion undergoes the most extensive sequence coverage by ETD. Primarily metallated and non-metallated c- and z-ions form for all peptides investigated. Metal adducted product ions are only present when at least half of the peptide sequence can be incorporated into the ion; this suggests that the metal ion simultaneously attaches to more than one acidic site. The only site consistently lacking dissociation is at the N-terminal side of a proline residue. Increasing peptide chain length generates more backbone cleavage for metal-peptide complexes with the same charge state. For acidic peptides with the same length, increasing the precursor ion charge state from 2+ to 3+ also leads to more cleavage. The results of this study indicate that highly acidic peptides can be sequenced by ETD of complexes formed with Pr(III). Copyright © 2017 John Wiley & Sons, Ltd.

Optical analysis of RE(3+) (RE = Pr(3) (+) , Er(3) (+) and Nd(3) (+) ):cadmium lead boro tellurite glasses.

This article reports on the optical characterization of Pr(3) (+) -, Er(3) (+) - and Nd(3) (+) -doped cadmium lead boro tellurite (CLBT) glasses prepared using the melt quenching method. The visible-near infrared (Vis-NIR) absorption spectra of these glasses were analyzed systematically. On measuring the NIR emission spectra of Er(3) (+) :CLBT glasses, a broad emission band centered at 1536 nm ((4) I13 /2  â†’ (4) I15 /2 ) was observed, as were three NIR emission bands at 900 nm ((4) F3 /2  â†’ (4) I9 /2 ), 1069 nm ((4) F3 /2  â†’ (4) I11 /2 ) and 1338 nm ((4) F3 /2  â†’ (4) I13 /2 ) from Nd(3) (+) :CLBT glasses and an NIR emission band at 1334 nm ((1) G4  â†’ (3) H5 ) from Pr(3) (+) :CLBT glasses at an excitation wavelength (λex ) of 514.5 nm (Ar(+) laser). Copyright © 2016 John Wiley & Sons, Ltd.

Functional near infrared-emitting Cr3+/Pr3+ co-doped zinc gallogermanate persistent luminescent nanoparticles with superlong afterglow for in vivo targeted bioimaging.

Near infrared (NIR)-emitting persistent luminescent nanoparticles (PLNPs) have great potential for in vivo bioimaging with the advantages of no need for in situ excitation, high signal-to-noise ratio, and deep tissue penetration. However, functional NIR-emitting PLNPs with long afterglow for long-term in vivo imaging are lacking. Here, we show the synthesis of NIR-emitting long-persistent luminescent nanoparticles (LPLNPs) Zn2.94Ga1.96Ge2O10:Cr(3+),Pr(3+) by a citrate sol-gel method in combination with a subsequent reducing atmosphere-free calcination. The persistent luminescence of the LPLNPs is significantly improved via codoping Pr(3+)/Cr(3+) and creating suitable Zn deficiency in zinc gallogermanate. The LPLNP powder exhibits bright NIR luminescence in the biological transparency window with a superlong afterglow time of over 15 days. A persistent energy transfer between host and Cr(3+) ion in the LPLNPs is observed and its mechanism is discussed. PEGylation greatly improves the biocompatibility and water solubility of the LPLNPs. Further bioconjugation with c(RGDyK) peptide makes the LPLNPs promising for long-term in vivo targeted tumor imaging with low toxicity.

Evaluation of intensity and energy interaction parameters for the complexation of Pr(III) with selected nucleoside and nucleotide through absorption spectral studies.

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 (ß), 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+).

Preparation of radioactive praseodymium oxide as a multifunctional agent in nuclear medicine: expanding the horizons of cancer therapy using nanosized neodymium oxide.

OBJECTIVE: Many studies have attempted to assess the significance of the use of the ß(-)particle emitter praseodymium-142 ((142)Pr) in cancer treatment. As praseodymium oxide (Pr(2)O(3)) powder is not water soluble, it was dissolved in HCl solution and the resultant solution had to be pH adjusted to be in an injectable radiopharmaceutical form. Moreover, it was shown that the nanosized neodymium oxide (Nd(2)O(3)) induced massive vacuolization and cell death in non-small-cell lung cancer. In this work, the production of (142)Pr was studied and water-dispersible nanosized Pr(2)O(3) was proposed to improve the application of (142)Pr in nuclear medicine. MATERIALS AND METHODS: Data from different databases pertaining to the production of (142)Pr were compared to evaluate the accuracy of the theoretical calculations. Water-dispersible nanosized Pr(2)O(3) was prepared using a poly(ethylene glycol) (PEG) coating or PEGylation method as a successful mode of drug delivery. Radioactive (142)Pr(2)O(3) was produced via a (142)Pr(n,γ)(142)Pr reaction by thermal neutron bombardment of the prepared sample. RESULTS: There was good agreement between the reported experimental data and the data based on nuclear model calculations. In addition, a small part of nano-Pr(2)O(3) particles remained in suspension and most of them settled out of the water. Interestingly, the PEGylated Pr(2)O(3) nanoparticles were water dispersible. After neutron bombardment of the sample, a stable colloidal (142)Pr(2)O(3) was formed. CONCLUSION: The radioactive (142)Pr(2)O(3) decays to the stable (142)Nd(2)O(3). The suggested colloidal (142)Pr(2)O(3) as a multifunctional therapeutic agent could have dual roles in cancer treatment as a radiotherapeutic agent using nanosized (142)Pr(2)O(3) and as an autophagy-inducing agent using nanosized (142)Nd(2)O(3).

Characteristics of the energy bands and the spectroscopic parameters of Pr3+ ions in PrCl3 mixed methanol, iso-propanol and butanol solutions.

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.

High-power direct green laser oscillation of 598 mW in Pr(3+)-doped waterproof fluoroaluminate glass fiber excited by two-polarization-combined GaN laser diodes.

We demonstrated a high-power and highly efficient Pr-doped waterproof fluoride glass fiber laser at 522.2 nm excited by two-polarization-combined GaN laser diodes and achieved a subwatt output power of 598 mW and slope efficiency of 43.0%. This system will enable us to make a vivid laser display, a photocoagulation laser for eye surgery, a color confocal scanning laser microscope, and an effective laser for material processing. Direct visible ultrashort pulse generation is also expected.

Dosimetric characterization of 142Pr glass seeds for brachytherapy.

A glass bead consisted of the beta(-)-emitting (142)Pr is proposed for brachytherapy treatment of prostate cancer. Appropriate radionuclide and seed dimensions were selected and sample seeds were manufactured. For the quantitative dosimetric parameters, two-dimensional dose distributions were calculated using the MCNP5 Monte Carlo code and measured using radiochromic film. The computational results compared well with measurements. Dose at 0.6 cm from the seed center can exceed 130 Gy. The reference dose rate, radial dose function and the anisotropy function were derived.

Calculation of electric dipole intensity parameters of 4f-4f transitions of Pr(III) and glutathione reduced (GSH) complex in presence and absence of Zn(II).

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).

Optical properties and upconversion in Pr3+ doped in aluminum, barium, calcium fluoride glass--I.

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.

Absorption spectroscopic study of synergistic extraction of praseodymium with benzoyl acetone in presence of crown ether.

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.

Comparison of energy interaction parameters for the complexation of Pr(III) with glutathione reduced (GSH) in absence and presence of Zn(II) in aqueous and aquated organic solvents using 4f-4f transition spectra as PROBE.

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.