Development of europium(III) complex functionalized silica nanoprobe for luminescence detection of tetracycline.

Increasing awareness of the health and environment impacts of the antibiotics misuse or overuse, such as tetracycline (TC) in treatment or prevention of infections and diseases, has driven the development of robust methods for their detection in biological, environmental and food systems. In this work, we report the development of a new europium(III) complex functionalized silica nanoprobe (SiNPs-Eu3+) for highly sensitive and selective detection of TC residue in aqueous solution and food samples (milk and meat). The nanoprobe is developed by immobilization of Eu3+ ion onto the surface of silica nanoparticles (SiNPs) as the emitter and TC recognition unit. The ß-diketone configuration of TC can further coordinate with Eu3+ steadily on the surface of nanoprobe, facilitating the absorption of light excitation for Eu3+ emitter activation and luminescence "off-on" response. The dose-dependent luminescence enhancement of SiNPs-Eu3+ nanoprobe exhibits good linearities, allowing the quantitative detection of TC. The SiNPs-Eu3+ nanoprobe shows high sensitivity and selectivity for TC detection in buffer solution. Time resolved luminescence analysis enables the elimination of autofluorescence and light scattering for highly sensitive detection of TC in milk and pork mince with high accuracy and precision. The successful development of SiNPs-Eu3+ nanoprobe is anticipated to provide a rapid, economic, and robust approach for TC detection in real world samples.

Enhanced biosorption of europium and cesium ions from aqueous solution onto phalaris seed peel as environmental friendly biosorbent: Equilibrium and kinetic studies.

The sorption characteristics of Eu(III) and Cs(I) removal from aqueous solution were estimated using phalaris seeds peel powder (PSP), a novel biosorbent that is economical and low-cost. Batch equilibrium experiments were carried out to investigate the effects of contact time, initial metal concentration, media pH, and interference ions on the sorption of Eu(III) and Cs(I). PSP powder characterization via Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG/DSC), X-ray diffraction (XRD), and scanning electron microscope (SEM) revealed some changes before and after the adsorption process. This indicates that most likely, adsorption has taken place between the metal ions and the adsorbents in the aqueous solution. The obtained results show that Eu(III) has a higher selectivity than Cs(I). The kinetics of the adsorption of Eu3+ and Cs+ have been discussed. It was shown that the second-order kinetic equation could describe the sorption and was found to be the best fitted model (R2 = 0.999) for two metal ions. Langmuir and, Dubinin-Radushkevich (D-R), isotherm were found to best fit (R2 = 0.99) in this study. The separation factor (RL) value of less than 1.0 indicates that the biosorption of both metal ions on PSP is favorable. Thermodynamic parameters, such as ΔHo, ΔGo, and ΔSo, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures. The obtained results indicated the endothermic nature of the sorption process for both metal ions onto PSP. PSP powder has the potential to be used as a low-cost biosorbent for the removal of Eu(III) and Cs(I) from wastewater, according to the findings.

Targeted Luminescent Europium Peptide Conjugates: Comparative Analysis Using Maleimide and para-Nitropyridyl Linkages for Organelle Staining.

The syntheses and photophysical behavior of nine strongly luminescent nonadentate Eu(III) complexes are reported. Each complex is based on N-functionalized 1,4,7-triazacyclononane, and linkage to other groups or targeting vectors can occur either via amide bond formation to a coordinated pyridine p-aminopropyl group or via a nucleophilic substitution reaction involving thiol attack on a metal coordinated p-nitropyridyl moiety. Evidence is presented in favor of the latter conjugation strategy, as parallel work with maleimide conjugates was complicated or compromised by the propensity to undergo post-conjugation thiol exchange or succinimide ring hydrolysis reactions. Confocal microscopy and spectral imaging studies revealed that the peptide conjugate of AcCFFKDEL was found to localize selectively in the endoplasmic reticulum of mouse fibroblast cells, whereas the related maleimide conjugate was only observed in cellular lysosomes.

Luminescence and Cationic-Size-Driven Site Selection of Eu3+ and Ce3+ Ions in Ca8Mg(SiO4)4Cl2.

In this work, the morphology, composition, crystal, and electronic structure of Ca8Mg(SiO4)4Cl2 (CMSOC) prepared by a high-temperature solid-state reaction technique are characterized first. To investigate the site occupancies of Eu3+ and Ce3+ in CMSOC, the emission spectra under well-chosen wavelength excitations and the corresponding excitation spectra by monitoring of the specific wavelength emissions are measured in detail for singly doped samples with different concentrations. Two kinds of Eu3+ or Ce3+ luminescence spectra are found. On the basis of the chemical environments of two Ca2+ sites and dielectric chemical bond theory, the sites of these two kinds of Eu3+ and Ce3+ luminescence spectra are respectively assigned. Because energy transfer between the two types of luminescent centers, concentration-dependent emission-wavelength shifting, and luminescence concentration quenching are negligible, the emission spectra of Eu3+ and Ce3+ give us a hint of their occupation preferences on two Ca2+ sites. The results indicate that, with an increase of the doping concentration, the Eu3+ ions with smaller cationic size show an occupation preference on the smaller Ca2+(1) sites, but the Ce3+ ions with larger cationic size are inclined to enter the larger Ca2+(2) sites. These opposite occupation preferences of Eu3+ and Ce3+ in CMSOC are thought to be the cationic-size-driven site selection.

Accumulation of 152+154Eu(III) by Aspergillus sydowii and Trichoderma harzianum.

Radionuclides-resistant filamentous fungi were isolated from radionuclides' contaminated soils. Effects of contact time, mycelia dosage, pH, ionic strength and thiol compounds on 152+154Eu(III) accumulation on two kinds of filamentous fungi (Aspergillus sydowii and Trichoderma harzianum, denoted as A. sydowii and T. harzianum, respectively) were investigated by batch techniques. The maximum tolerance to Eu(III) concentration of A. sydowii and T. harzianum reached 3000 mg/L and 3500 mg/L, and the Eu(III) accumulation on A. sydowii and T. harzianum can be fitted better with the pseudo-second-order kinetic model, respectively. Filamentous fungi were characterized by FT-IR and acid base titrations, and morphological structures of mycelia changed obviously under Eu(III) stress by SEM and TEM analysis. The results suggested that filamentous fungi could play an important role in the migration and transformation of radionuclides in the environment.

Coagulation behavior of humic acid in aqueous solutions containing Cs+, Sr2+ and Eu3+: DLS, EEM and MD simulations.

The coagulation behaviors of humic acid (HA) with Cs+ (10-500 mM), Sr2+ (0.8-10.0 mM) and Eu3+ (0.01-1.0 mM) at different pH values (2.8, 7.1 and 10.0) were acquired through a dynamic light scattering (DLS) technique combined with spectroscopic analysis and molecular dynamic (MD) simulations. The coagulation rate and the average hydrodynamic diameter () increased significantly as the concentration of nuclides increased. could be scaled to time t as ∝ ta at higher Sr2+ concentrations, which shows that HA coagulation is consistent with the diffusion-limited colloid aggregation (DLCA) model. Trivalent Eu3+ induced HA coagulation at a much lower concentration than bivalent Sr2+ and monovalent Cs+. The coagulation value ratio of Sr2+ and Eu3+ to Cs+ is almost proportional to Z-6, indicating that the HA coagulation process is generally consistent with the Schulze-Hardy rule. Spectroscopic analysis indicated that the complexation between nuclides and carboxylic/phenolic groups of HA molecules played important roles in the coagulation of HA. MD modelling suggested that Sr2+ and Eu3+ ions increased the coagulation process through the formation of intra- or inter-molecular bridges between negatively charged HA molecules, whereas for Cs+, no inter-molecular bridges were formed. This work offers new insight into the interactions between HA and radionuclides and provides a prediction for the roles of HA in the transportation and elimination of radionuclides in severely polluted environments.

Synthesis of europium-doped VSOP, customized enhancer solution and improved microscopy fluorescence methodology for unambiguous histological detection.

BACKGROUND: Intrinsic iron in biological tissues frequently precludes unambiguous the identification of iron oxide nanoparticles when iron-based detection methods are used. Here we report the full methodology for synthesizing very small iron oxide nanoparticles (VSOP) doped with europium (Eu) in their iron oxide core (Eu-VSOP) and their unambiguous qualitative and quantitative detection by fluorescence. METHODS AND RESULTS: The resulting Eu-VSOP contained 0.7 to 2.7% Eu relative to iron, which was sufficient for fluorescent detection while not altering other important particle parameters such as size, surface charge, or relaxivity. A customized enhancer solution with high buffer capacity and nearly neutral pH was developed to provide an antenna system that allowed fluorescent detection of Eu-VSOP in cells and histologic tissue slices as well as in solutions even under acidic conditions as frequently obtained from dissolved organic material. This enhancer solution allowed detection of Eu-VSOP using a standard fluorescence spectrophotometer and a fluorescence microscope equipped with a custom filter set with an excitation wavelength (λex) of 338 nm and an emission wavelength (λem) of 616 nm. CONCLUSION: The fluorescent detection of Eu-doped very small iron oxide nanoparticles (Eu-VSOP) provides a straightforward tool to unambiguously characterize VSOP biodistribution and toxicology at tissue, and cellular levels, providing a sensitive analytical tool to detect Eu-doped IONP in dissolved organ tissue and biological fluids with fluorescence instruments.

A luminescent lanthanide approach towards direct visualization of primary cilia in living cells.

We report a direct imaging tool, HGEu001, for primary cilia in living cells, which is specific, and based on the UV light or near infrared laser (via two-photon excitation) induced long-lived europium luminescence.

Spectral investigations on Eu3+ ,Sm3+ -doped and Sm3+ /Eu3+ co-doped potassium-fluoro-phosphate glass emitting intense orange-red for lighting applications.

Potassium fluoro-phosphate (KFP) glass singly doped with different concentrations of europium (Eu3+ ) or samarium (Sm3+ ) or co-doped (Sm3+ /Eu3+ ) was prepared, and their luminescence spectra were investigated. The phase composition of the product was verified by X-ray diffraction analysis. Optical transition properties of Eu3+ in the studied potassium phosphate glass were evaluated in the framework of the Judd-Ofelt theory. The radiative transition rates (AR ), fluorescence branching ratios (ß), stimulated emission cross-sections (σe ) and lifetimes (τexp ) for certain transitions or levels were evaluated. Red emission of Eu3+ was exhibited mainly by the 5 D0 →7 F2 transition located at 612 nm. Concentration quenching and energy transfer were observed from fluorescence spectra and decay curves, respectively. It was found that the lifetimes of the 5 D0 level increased with increase in concentration and then decreased. By co-doping with Sm3+ , energy transfer from Sm3+ to Eu3+ occurred and contributed to the enhancement in emission intensity. Intense orange-red light emission was obtained upon sensitizing with Sm3+ in KFP glass. This approach shows significant promise for use in reddish-orange lighting applications. The optimized properties of the Sm3+ /Eu3+ co-doped potassium phosphate glass might be promising for optical materials.

Simultaneous quantification of iodine and high valent metals via ICP-MS under acidic conditions in complex matrices.

The determination of iodine as a main fission product (especially the isotopes I-129 and I-131) of stored HLW in a disposal beside its distribution as a natural ingredient of many different products like milk, food and seawater is a matter of particular interest. The simultaneous ICP-MS determination of iodine as iodide together with other elements (especially higher valent metal ions) relevant for HLW is analytically very problematic. A reliable ICP-MS quantification of iodide must be performed at neutral or alkaline conditions in contrast to the analysis of metal ions which are determined in acidic pH ranges. Herein, we present a method to solve this problem by changing the iodine speciation resulting in an ICP-MS determination of iodide as iodate. The oxidation from iodide to iodate with sodium hypochlorite at room temperature is a fast and convenient method with flexible reaction time, from one hour up to three days, thus eliminating the disadvantages of quantifying iodine species via ICP-MS. In the analysed concentration range of iodine (0.1-100µgL-1) we obtain likely quantitative recovery rates for iodine between 91% and 102% as well as relatively low RSD values (0.3-4.0%). As an additional result, it is possible to measure different other element species in parallel together with the generated iodate, even high valent metals (europium and uranium beside caesium) at recovery rates in the same order of magnitude (93-104%). In addition, the oxidation process operates above pH 7 thus offering a wide pH range for sample preparation. Even analytes in complex matrices, like 5M saline (NaCl) solution or artificial cement pore water (ACW) can be quantified with this robust sample preparation method.

Measurement analysis of two radials with a common-origin point and its application.

In spectral analysis, a chemical component is usually identified by its characteristic spectra, especially the peaks. If two components have overlapping spectral peaks, they are generally considered to be indiscriminate in current analytical chemistry textbooks and related literature. However, if the intensities of the overlapping major spectral peaks are additive, and have different rates of change with respect to variations in the concentration of the individual components, a simple method, named the 'common-origin ray', for the simultaneous determination of two components can be established. Several case studies highlighting its applications are presented.

Effects of Organic Acids and Sylvite on Phytoextraction of 241Am Contaminated Soil.

Contamination of soil with Americium (241Am) at nuclear sites in China poses a serious problem. We screened six plants, from five families, for their 241Am-enrichment potential. Europium (Eu), which is morphologically and chemically similar to the highly toxic 241Am, was used in its place. Moreover, the effects of sylvite, citric acid (CA), malic acid (MA), and humic acid (HA) on the absorption of 241Am by the plants, and its transport within them, were evaluated along with their effect on plant biomass and 241Am extraction volume. Barley and cabbage showed relatively stronger Eu accumulation capacities. Citric acid promoted the absorption of 241Am by barley roots and its transport within the plants. The effects of sylvite were not obvious and those of HA were the weakest in case of sunflower; HA, however, maximally increased the biomass of the plants. Our results could provide the basis for future radionuclide phytoremediation of contaminated soils.

A lysosome targetable luminescent bioprobe based on a europium ß-diketonate complex for cellular imaging applications.

Herein, we report a novel lysosome targetable luminescent bioprobe derived from a europium coordination compound, namely Eu(pfphOCH3IN)3(DDXPO) 4 [where HpfphOCH3IN = 4,4,5,5,5-pentafluoro-3-hydroxy-1-(1-(4-methoxyphenyl)-1H-indol-3-yl)pent-2-en-1-one and DDXPO = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide]. Notably, the newly designed europium complex exhibits significant quantum yield (Φoverall = 25 ± 3%) and 5D0 excited state lifetime (τ = 398 ± 3 µs) values under physiological pH (7.2) conditions when excited at 405 nm. Hence the developed europium complex has been evaluated for live cell imaging applications using mouse pre-adipocyte cell lines (3T3L1). Colocalization studies of the designed bio-probe with commercial Lysosome-GFP in 3T3L1 cells demonstrated the specific localization of the probe in the lysosome with a high colocalization coefficient (A = 0.83). Most importantly, the developed bioprobe exhibits good cell permeability, photostability and non-cytotoxicity.

A hydrometallurgical process for the recovery of terbium from fluorescent lamps: Experimental design, optimization of acid leaching process and process analysis.

Terbium and rare earths recovery from fluorescent powders of exhausted lamps by acid leaching with hydrochloric acid was the objective of this study. In order to investigate the factors affecting leaching a series of experiments was performed in according to a full factorial plan with four variables and two levels (42). The factors studied were temperature, concentration of acid, pulp density and leaching time. Experimental conditions of terbium dissolution were optimized by statistical analysis. The results showed that temperature and pulp density were significant with a positive and negative effect, respectively. The empirical mathematical model deducted by experimental data demonstrated that terbium content was completely dissolved under the following conditions: 90 °C, 2 M hydrochloric acid and 5% of pulp density; while when the pulp density was 15% an extraction of 83% could be obtained at 90 °C and 5 M hydrochloric acid. Finally a flow sheet for the recovery of rare earth elements was proposed. The process was tested and simulated by commercial software for the chemical processes. The mass balance of the process was calculated: from 1 ton of initial powder it was possible to obtain around 160 kg of a concentrate of rare earths having a purity of 99%. The main rare earths elements in the final product was yttrium oxide (86.43%) following by cerium oxide (4.11%), lanthanum oxide (3.18%), europium oxide (3.08%) and terbium oxide (2.20%). The estimated total recovery of the rare earths elements was around 70% for yttrium and europium and 80% for the other rare earths.

Eu(III)-Fulvic Acid Complexation: Evidence of Fulvic Acid Concentration Dependent Interactions by Time-Resolved Luminescence Spectroscopy.

Europium speciation is investigated by time-resolved luminescence spectroscopy (TRLS) in the presence of Suwannee River fulvic acid (SRFA). From complexation isotherms built at different total Eu(III) concentrations, pH values, ionic strength, and SRFA concentrations, it appears that two luminescence behaviors of Eu(III) are occurring. The first part, at the lowest CSRFA values, is showing the typical luminescence evolution of Eu(III) complexed by humic substances--that is, the increase of the asymmetry ratio between the (5)D0 → (7)F2 and (5)D0 → (7)F1 transitions up to a plateau--, and the occurrence of a biexponential decay--the first decay being faster than free Eu(3+). At higher CSRFA, a second luminescence mode is detected as the asymmetry ratio is increasing again after the previous plateau, and could correspond to the formation of another type of complex, and/or it can reflect a different spatial organization of complexed europium within the SRFA structure. The luminescence decay keeps on evolving but link to hydration number is not straightforward due to quenching mechanisms. The Eu(III) chemical environment evolution with CSRFA is also ionic strength dependent. These observations suggest that in addition to short-range interactions--intraparticulate complexation--, there might be interactions at longer range--interparticulate repulsion--between particles that are complexing Eu(III) at high CSRFA. These interactions are not yet accounted by the different complexation models.

Macroscopic and Microscopic Investigation of U(VI) and Eu(III) Adsorption on Carbonaceous Nanofibers.

The adsorption mechanism of U(VI) and Eu(III) on carbonaceous nanofibers (CNFs) was investigated using batch, IR, XPS, XANES, and EXAFS techniques. The pH-dependent adsorption indicated that the adsorption of U(VI) on the CNFs was significantly higher than the adsorption of Eu(III) at pH < 7.0. The maximum adsorption capacity of the CNFs calculated from the Langmuir model at pH 4.5 and 298 K for U(VI) and Eu(III) were 125 and 91 mg/g, respectively. The CNFs displayed good recyclability and recoverability by regeneration experiments. Based on XPS and XANES analyses, the enrichment of U(VI) and Eu(III) was attributed to the abundant adsorption sites (e.g., -OH and -COOH groups) of the CNFs. IR analysis further demonstrated that -COOH groups were more responsible for U(VI) adsorption. In addition, the remarkable reducing agents of the R-CH2OH groups were responsible for the highly efficient adsorption of U(VI) on the CNFs. The adsorption mechanism of U(VI) on the CNFs at pH 4.5 was shifted from inner- to outer-sphere surface complexation with increasing initial concentration, whereas the surface (co)precipitate (i.e., schoepite) was observed at pH 7.0 by EXAFS spectra. The findings presented herein play an important role in the removal of radionuclides on inexpensive and available carbon-based nanoparticles in environmental cleanup applications.

Evaluation of Eu(II) -based positive contrast enhancement after intravenous, intraperitoneal, and subcutaneous injections.

Eu(II) -based contrast agents offer physiologically relevant, metal-based redox sensing that is unachievable with Gd(III) -based contrast agents. To evaluate the in vivo contrast enhancement of Eu(II) as a function of injection type, we performed intravenous, intraperitoneal, and subcutaneous injections in mice. Our data reveal a correlation between reported oxygen content and expected rates of diffusion with the persistence of Eu(II) -based contrast enhancement. Biodistribution studies revealed europium clearance through the liver and kidneys for intravenous and intraperitoneal injections, but no contrast enhancement was observed in organs associated with clearance. These data represent a step toward understanding the behavior of Eu(II) -based complexes in vivo. Copyright © 2016 John Wiley & Sons, Ltd.

Rare earth elements in core marine sediments of coastal East Malaysia by instrumental neutron activation analysis.

A study was carried out on the concentration of REEs (Dy, Sm, Eu,Yb, Lu, La and Ce) that are present in the core marine sediments of East Malaysia from three locations at South China Sea and one location each at Sulu Sea and Sulawesi Sea. The sediment samples were collected at a depth of between 49 and 109 m, dried, and crushed to powdery form. The entire core sediments prepared for Instrumental Neutron Activation Analysis (INAA) were weighted approximately 0.0500 g to 0.1000 g for short irradiation and 0.1500 g to 0.2000 g for long irradiation. The samples were irradiated with a thermal neutron flux of 4.0×10(12) cm(-2) s(-1) in a TRIGA Mark II research reactor operated at 750 kW. Blank samples and standard reference materials SL-1 were also irradiated for calibration and quality control purposes. It was found that the concentration of REEs varies in the range from 0.11 to 36.84 mg/kg. The chondrite-normalized REEs for different stations suggest that all the REEs are from similar origins. There was no significant REEs contamination as the enrichment factors normalized for Fe fall in the range of 0.42-2.82.

Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay.

Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay, proposed as a backfill material in the Indian geological repository, was studied using the out-diffusion method. Radiotracers (22)Na, (137)Cs, (85)Sr and (154)Eu were used; the first three are carrier-free enabling experimental work at sub-micromolar metal ion concentration, and Eu(III) tracer (154)Eu was used at sub millimolar concentration. An out-diffusion methodology, wherein a thin planar source of radioactivity placed between two clay columns diffuses out, was used to obtain the apparent diffusion coefficient (Da) values. This methodology enabled determination of diffusion coefficient even for strongly sorbing (154)Eu. Da values for (22)Na, (137)Cs, (85)Sr and (154)Eu were 2.35 (±0.14) × 10(-11), 2.65 (±0.09) × 10(-12), 3.32 (±0.15) × 10(-11) and 1.23 (±0.15) × 10(-13) m(2) s(-1), respectively. Da values were found to be in fair agreement with literature data reported for similar mineralogical sediments. Sorption of radionuclides on the clay was also determined in the present study and differences in Da values were rationalized on the basis of sorption data. Distribution ratios (Kd) for Cs(I) and Eu(III) were higher than that for Sr(II), which in turn was higher than that for Na(I).

Utilization of natural hematite as reactive barrier for immobilization of radionuclides from radioactive liquid waste.

Potential utilization of hematite as a natural material for immobilization of long-lived radionuclides from radioactive liquid waste was investigated. Hematite ore has been characterized by different analytical tools such as Fourier transformer infrared (FTIR), X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal (DT) analysis, scanning electron microscopy (SEM) and BET-surface area. In this study, europium was used as REEs(III) and as a homolog of Am(III)-isotopes (such as (241)Am of 432.6 y, (242m)Am of 141 y and (243)Am of 7370 y). Micro particles of the hematite ore were used for treatment of radioactive waste containing (152+154)Eu(III). The results indicated that 96% (4.1 × 10(4) Bq) of (152+154)Eu(III) was efficiently retained onto hematite ore. Kinetic experiments indicated that the processes could be simulated by a pseudo-second-order model and suggested that the process may be chemisorption in nature. The applicability of Langmuir, Freundlich and Temkin models was investigated. It was found that Langmuir isotherm exhibited the best fit with the experimental results. It can be concluded that hematite is an economic and efficient reactive barrier for immobilization of long-lived radio isotopes of actinides and REEs(III).