Rapid and reliable ratiometric fluorescence detection of nitro explosive 2,4,6-trinitrophenol based on a near infrared (NIR) luminescent Zn(II)-Nd(III) nanoring.

Rapid and quantitative detection of 2,4,6-trinitrophenol (TNP) is very crucial for homeland security, military application, and environment protection. Herein, a nine-metal Zn(II)-Nd(III) nanoring 1 with a diameter of 2.3 nm was constructed by the use of a long-chain Schiff base ligand, which shows ratiometric fluorescence response to TNP with high selectivity and sensitivity. The fluorescence sensing behavior of 1 to TNP is expressed by a first-order equation I1060nm/I560nm = -0.0128*[TNP] + 0.9723, which can be used to quantitatively analyze TNP concentrations in solution. The limits of detection (LODs) to TNP based on the ligand-centered (LC) and Nd(III) emissions of 1 are 5.93 µM and 3.18 µM, respectively. The fluorescence response mechanism to TNP is attributed to the competitive absorption effect and photoinduced electron transfer (PET). The luminescence quenching of 1 is dominated by static process.

Composite Resins Impregnated by Phosphorus Organic Extractants for Separation of Rare Earth Elements from Nitrate-Based Leachate of Permanent Magnets.

Composite resins impregnated by different organophosphorus extractants were developed and used for the extraction chromatography recovery of rare earth elements from nitrate-based leachate of NdFeB permanent magnets. The influence of different factors on recovery of Nd(III) and Fe(III), as the most difficult to separate elements, by developed resins was studied. The influence of extractant structure, the composition of feed solutions, and concentrations of HNO3 and NH4NO3 on the recovery of Fe(III) and Nd(III) by prepared resins were considered. The best recovery of Nd(III) was shown by resin impregnated with N,N-dioctyl (diphenylphosphoryl) acetamide. For this material, sorption characteristics (values of the distribution coefficient, capacity, and the Nd(III)/Fe(III) separation factor) were obtained, and the reproducibility of the loading-stripping process was evaluated. This resin and its precursors were characterized by IR spectroscopy. It was found that the developed resin is more efficient for Nd(III) recovery than resin impregnated with TODGA. An effective approach to the Nd(III)/Fe(III) separation with developed resin in nitrate solution was proposed. This approach was used for recovery of Pr(III), Nd(III), and Dy(III) from the nitrate-based leachate of NdFeB magnets by the developed resin. The final product contained 99.6% of rare earths.

Optical Amplification at 637 and 1067 nm Based on Organic Molecule AQ(PhDPA)2 and NdIII Complex Codoped Polymer Waveguides.

Based on the molecular energy transfer mechanism, relative gains at 1067 and 637 nm wavelengths are achieved in thermally activated delayed fluorescence molecule AQ(PhDPA)2 and Nd complex with chelating phosphine oxide as ligands codoped polymer waveguides, with the excitation of low-power UV light-emitting diodes (LEDs) instead of traditional semiconductor lasers as pump sources. For AQ(PhDPA)2 -Nd(DBTTA)3 (DBFDPO) (DBTTA = dibenzotetrathienoacene, DBFDPO = 4,6-bis (diphenylphosphoryl) dibenzofuran) -codoped polymethylmethacrylate (PMMA), and AQ(PhDPA)2 -Nd(DBTTA)3 (FDPO) (FDPO = 9,9-bis (diphenylphosphorylphenyl) fluorene)-codoped PMMA polymers with a mass ratio of 1:4 respectively, when they are spin-coated as upper claddings, the relative gains of 2.2 and 1.8 dB cm-1 at 1067 nm are obtained in evanescent-field waveguides with cross-section of 4 × 8 µm2 under excitation of 300 mW 405 nm LED, and the gains of 3.9 and 4.9 dB cm-1 at 637 nm are achieved with pumping of 530 mW 450 nm LED respectively. By growing a 100 nm-thick aluminum reflector with the waveguides, the optical gain at 1067 and 637 nm can be enhanced to 3.5 and 6.1 dB cm-1 , corresponding to AQ(PhDPA)2 -Nd(DBTTA)3 (DBFDPO) and AQ(PhDPA)2 -Nd(DBTTA)3 (FDPO)-codoped PMMA polymers, respectively.

Theoretical and Experimental Vibrational Characterization of Biologically Active Nd(III) Complex.

The neodymium(III) complex of orotic acid (HOA) was synthesized and its structure determined by means of analytical and spectral analyses. Detailed vibrational analysis of HOA, sodium salt of HOA, and Nd(III)-OA systems based on both the calculated and experimental spectra confirmed the suggested metal-ligand binding mode. Significant differences in the IR and Raman spectra of the complex were observed as compared to the spectra of the ligand. The calculated vibrational wavenumbers, including IR intensities and Raman scattering activities, for the ligand and its Nd(III) complex were in good agreement with the experimental data. The vibrational analysis performed for the studied species, orotic acid, sodium salt of orotic acid, and its Nd(III) complex helped to explain the vibrational behaviour of the ligand's vibrational modes, sensitive to interaction with Nd(III). In this paper we also report preliminary results about the cytotoxicity of the investigated compounds. The cytotoxic effects of the ligand and its Nd(III) complex were determined using the MTT method on different tumour cell lines. The screening performed revealed that the tested compounds exerted cytotoxic activity upon the evaluated cell lines.

Nd(III) hypersensitive peak as an optical absorption probe for determining nitric acid in aqueous solution: An application to aqueous raffinate solutions in nuclear reprocessing.

A new method using Nd(III) absorption peak as a probe is described for the measurement of nitric acid concentration in aqueous solution. The hypersensitive peak of Nd(III) at 575.1 nm shows a substantial enhancement in the absorbance in comparison to other absorption peaks with increasing nitric acid concentration. The integrated area and absorbance of this hypersensitive peak show a linear dependency over a large dynamic range of 0.5-15.5 M of nitric acid. A methodology for the correction of spectral interference to the probing absorption peak of Nd(III) is also reported. The method is applied for the measurement of nitric acid in synthetic high level liquid waste solution and shown to be comparable to that obtained by titrimetric method. The present method can be easily adopted for the measurement of nitric acid concentration in aqueous raffinate solutions of nuclear reprocessing streams.

Solvent-Impregnated Resins Based on the Mixture of (2-Diphenylphosphoryl)-4-ethylphenoxy)methyl) diphenylphosphine Oxide and Ionic Liquid for Nd(III) Recovery from Nitric Acid Media.

Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene-divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C4mim]+[Tf2N]-for the extraction chromatography recovery of Nd(III) from nitric acid solutions. It was shown that introduction of the ionic liquid into the SIR composition results in considerable enhancement of the Nd(III) recovery efficiency compared with resin impregnated only by L in slightly acidic media. The influence of the L: ionic liquid molar ratio in the SIRs composition, their percentages, concentration of metal and HNO3 in the eluent, and acid type on the value of synergistic effect and adsorption efficiency of Nd(III) recovery was studied. The SIR containing 40% of mixture of L and [C4mim]+[Tf2N]- with molar ratio 2:1 turned out to be the most efficient. The selectivity of Nd(III) separation from light and heavy rare-earth elements was studied and the optimal conditions of Nd(III) adsorption recovery and stripping by this SIR were chosen. It was found that in recovery efficiency of Nd(III) developed SIR exceeded the SIR containing Cyanex 923 (a mixture of monodentate trialkylphosphine oxides) and [C4mim]+[Tf2N]-.

Three-dimensional macroporous wood-based selective separation membranes decorated with well-designed Nd(III)-imprinted domains: A high-efficiency recovery system for rare earth element.

Three-dimensional (3D) basswood materials, for the first time, were successfully used for the construction of rare-earth Nd(III)-imprinted nanocomposite membranes. Herein, polydopamine (PDA)-modified layers could be initially synthesized on basswood surfaces. After the double-bonded modification procedure, the 3D wood-based ionic imprinted membranes (3DW-IIMs) system was finally accomplished by developing a re-modified two-step-temperature free radical polymerization process. The as-design PDA@basswood surface structure was first proposed and applied as imprinting-initiated factors for the preparation of Nd(III)-imprinted sites. Importantly, excellent rebinding capacity (120.87 mg g-1), adsorption kinetics and permselectivity coefficients (more than 10) were achieved successfully. Furthermore, an important research result had also been found that the PDA-modified layers caused significant promotions to the rebinding capacities of the as-prepared 3DW-IIMs, that is to say, more and more Nd(III)-imprinted sites could be synthesized because of the PDA-modified surfaces. The as-obtained selective rebinding and separation results together with the green natural wood-based materials strongly demonstrated that our synthesis methodology of 3DW-IIMs had great potential for applications in various fields of rare earth separation, chemical industry, and environment protection.

Evaluation of DNA, BSA binding, and antimicrobial activity of new synthesized neodymium complex containing 29-dimethyl 110-phenanthroline.

In order to evaluate biological potential of a novel synthesized complex [Nd(dmp)2Cl3.OH2] where dmp is 29-dimethyl 110-phenanthroline, the DNA-binding, cleavage, BSA binding, and antimicrobial activity properties of the complex are investigated by multispectroscopic techniques study in physiological buffer (pH 7.2).The intrinsic binding constant (Kb) for interaction of Nd(III) complex and FS-DNA is calculated by UV-Vis (Kb = 2.7 ± 0.07 × 105) and fluorescence spectroscopy (Kb = 1.13 ± 0.03 × 105). The Stern-Volmer constant (KSV), thermodynamic parameters including free energy change (ΔG°), enthalpy change (∆H°), and entropy change (∆S°), are calculated by fluorescent data and Vant' Hoff equation. The experimental results show that the complex can bind to FS-DNA and the major binding mode is groove binding. Meanwhile, the interaction of Nd(III) complex with protein, bovine serum albumin (BSA), has also been studied by using absorption and emission spectroscopic tools. The experimental results show that the complex exhibits good binding propensity to BSA. The positive ΔH° and ∆S° values indicate that the hydrophobic interaction is main force in the binding of the Nd(III) complex to BSA, and the complex can quench the intrinsic fluorescence of BSA remarkably through a static quenching process. Also, DNA cleavage was investigated by agarose gel electrophoresis that according to the results cleavage of DNA increased with increasing of concentration of the complex. Antimicrobial screening test gives good results in the presence of Nd(III) complex system.