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The thermodynamic stability of rare earth (RE) materials plays a key role in the design of separation and recycling processes for RE elements. Thermodynamic stability is fundamentally influenced by the lanthanide contraction, as observed in the systematic reduction of unit cell volumes with increasing atomic number. RE materials are found in the form of solids having primary bonds in three dimensions (3D materials) as well as ones with primary bonds in two dimensions (2D materials) whose layers are held together by weak van der Waals (vdW) forces. While studies of synthesis, structure, and physical properties of 2D RE materials are numerous, no systematic research has compared their thermodynamic stability to that of 3D materials. In the present work, RE oxychlorides (REOCls), which display a structural transition from a 3D-polyhedral network (PbFCl-type) to a vdW-bonded layered one (SmSI-type) as the RE size decreases, were all synthesized by the flux method. High-temperature oxide melt solution calorimetry was used to determine their formation enthalpies to enable Born-Haber cycles to calculate lattice energies. Our results indicate that REOCl compounds are thermodynamically stable when compared to their binary oxides and chlorides. The lattice energies of 3D REOCls increase with decreasing RE size yet are insensitive to unit cell volumes for 2D REOCls. This is caused by interatomic interactions parallel and perpendicular to layers in the SmSI-type REOCls, causing a different structure response to the lanthanide contraction than 3D RE materials.

Biocement formed through microbially induced calcium carbonate precipitation (MICP) is an emerging biotechnology focused on reducing the environmental impact of concrete production. In this system, CO

Fluorescence-guided surgery (FGS) is an emerging technique for tissue visualization during surgical procedures. Structures of interest are labeled with exogenous probes whose fluorescent emissions are acquired and viewed in real-time with optical imaging systems. This study investigated rare-earth-doped albumin-encapsulated nanocomposites (REANCs) as short-wave infrared emitting contrast agents for FGS. Experiments were conducted using an animal model of 4T1 breast cancer. The signal-to-background ratio (SBR) obtained with REANCs was compared to values obtained using indocyanine green (ICG), a near-infrared dye used in clinical practice. Prior to resection, the SBR for tumors following intratumoral administration of REANCs was significantly higher than for tumors injected with ICG. Following FGS, evaluation of fluorescence intensity levels in excised tumors and at the surgical bed demonstrated higher contrast between tissues at these sites with REANC contrast than ICG. REANCs also demonstrated excellent photostability over 2 hours of continuous illumination, as well as the ability to perform FGS under ambient lighting, establishing these nanocomposites as a promising contrast agent for FGS applications.

Epitaxial thin and thick lead zirconate titanate (PZT) films with the composition of PbZr0.7Ti0.3O3 were grown onto single-crystal SrTiO3 (100), (111), and (110) substrates using both microwave and conventional hydrothermal methods at 90–180°C from amorphous Zr-Ti hydrous oxide and lead acetate precursors. Different bases, such as KOH, NaOH, and tetramethylammonium hydroxide pentahydrate (TMAH) were used to study the effect of mineralizer type on the film quality and morphology. The impact of substrate surface modification on PZT nucleation and film growth was examined through chemical etching or pre-coating the substrate with a RF-sputtered thin PZT layer. Thick PZT film (~27 µm in thickness) was successfully synthesized by periodic replenishment of the reaction nutrient. Moreover, according to the collected kinetic data for microwave hydrothermal reactions, a microwave continuous-flow reactor operating at ≈ 300°C may be used to grow PZT films with the thickness of the order of 1 mm.

Current methods of rare earth element (REE) recovery from industrial solutions are environmentally untenable and have significant waste management challenges. Increasing global REE consumption necessitates the development of new, sustainable means of production. Herein, we report a means of recovering aqueous REEs using monoethanolamine and carbon dioxide as predicted using the Mixed-Solvent Electrolyte thermodynamic model. Validation experiments have demonstrated the > 99% recovery of Nd3+ as its normal carbonate, with the filtrate containing monoethanolamine hydrogen chloride. Additional experimentation also demonstrated the > 99% recovery of aqueous La3+ and Y3+ as their respective normal carbonates. These findings demonstrate that a thermodynamic simulation engine may be used to decrease the number of empirically driven experiments required to develop a new, high yield REE recovery unit operation that is applicable to concentrated and dilute aqueous solutions typical of industrial streams.

Leaching of six individual rare earth (yttrium, cerium, neodymium, samarium, europium, and ytterbium) doped synthetic phosphogypsum samples using a suite of lixiviants was conducted. The lixiviants chosen for this study were phosphoric acid, sulfuric acid, gluconic acid, and a “biolixiviant” consisting of spent medium containing organic acids from the growth of the bacterium Gluconobacter oxydans on glucose. The biolixiviant had a pH of 2.1 and the dominant organic acid was determined to be gluconic acid, present at a concentration of 220 mM. The leaching behaviors of the studied lixiviants were compared and rationalized by thermodynamic simulations. The results suggest that at equivalent molar concentrations of 220 mM the biolixiviant was more efficient at rare earth element (REE) extraction than gluconic acid and phosphoric acid but less efficient than sulfuric acid. Unlike the organic acids, at pH 2.1 the mineral acids failed to extract REE, likely due to different complexation and kinetic effects.

A thermodynamic model has been developed for calculating the phase behavior and caloric properties of rare earth elements in multicomponent sulfate solutions over wide ranges of temperature (up to 300 °C) at concentrations extending to solid–liquid saturation. The model has been constructed using the previously developed Mixed-Solvent Electrolyte (MSE) framework, which combines the standard-state thermochemical properties of aqueous and solid species with an ion-interaction formulation for the excess Gibbs energy. The model accurately reproduces the properties of binary aqueous rare earth sulfate solutions and multicomponent systems that include sulfuric acid and/or sodium sulfate. Solid-liquid phase diagrams have been constructed to elucidate the solubility of both stable and metastable solid phases. Regularities in the solubility behavior have been identified as a function of the cation radius for rare earth sulfates and double sodium-rare earth sulfate salts. The solubility of rare earth sulfates at ambient conditions shows an s-shape pattern with a local maximum at Pr, followed by a plateau between Sm and Tb and then an increase starting from Tb. On the other hand, the double salts REE2Na2(SO4)4 show a solubility minimum at Pr, followed by a strong increase in solubility for heavier rare earths. For the double sulfate salts for which no experimental data are available, solubilities have been estimated using an analysis of trends in thermochemical properties across the lanthanide series. The model is part of a systematic effort to develop a comprehensive treatment of the properties of rare earth salt solutions to facilitate the design and optimization of processes for the recovery of rare earth elements.

Recycling electronic scrap is a significant source of rare earth metals. Whereas traditional recycling routes for some electronic scrap emphasize the recovery of silver and gold, value can be attained by recovering of rare earth elements from unique feed streams. This paper describes a hydrometallurgical process for the recovery of rare earth elements from hard disk drives using HCl as a re-usable extraction medium. The mixture was selectively leached using HCl to remove the magnet alloy coating from shredded hard disk drives. The dissolved rare earth elements were precipitated using sodium sulfate, recovered as the sodium double salt, and subsequentially converted to hydroxides. The recovery of rare earth elements is consistent with amounts predicted using a thermodynamic model based on the MSE (Mixed-Solvent Electrolyte) framework of precipitated double salts. The effect of HCl concentration was measured upon the magnet dissolution rate. In addition, the leaching rates for steel were evaluated and found to be three orders of magnitude lower than the magnet alloy. An automated system was used to control leachate pH. The magnet and steel dissolution rate were examined for various HCl concentrations. The recovery of rare earth hydroxides was over 80%.

Sodium rare earth fluorides, NaREF4 (RE = rare earth), are used as luminescent materials for light emission and biomedical applications and are important compositions for extracting and separating RE elements. Solution calorimetric measurements of a series of β-structured NaREF4 (Na1.5RE1.5F6) phases with various RE elements determined their heats of formation. Though the lattice contracts from light to heavy RE elements, NaREF4 compounds show more exothermic enthalpies of formation from binary components with decrease of RE3+ radius, contrary to behavior seen in most RE oxide ternary compounds. By constructing Born–Haber cycles, the different slopes of lines relating lattice energies to lattice parameters in binary and ternary fluorides appear to be the reason for this reverse trend, which can be associated with changes in the coordination number of RE cations. These trends and the metastability of sodium light RE fluorides not only reveal the key role of ionic radius in RE compound stability, but also are significant for the design and synthesis of new materials and motivate the more effective utilization of RE.

Background The ability to detect tumor-specific biomarkers in real-time using optical imaging plays a critical role in preclinical studies aimed at evaluating drug safety and treatment response. In this study, we engineered an imaging platform capable of targeting different tumor biomarkers using a multi-colored library of nanoprobes. These probes contain rare-earth elements that emit light in the short-wave infrared (SWIR) wavelength region (900–1700 nm), which exhibits reduced absorption and scattering compared to visible and NIR, and are rendered biocompatible by encapsulation in human serum albumin. The spectrally distinct emissions of the holmium (Ho), erbium (Er), and thulium (Tm) cations that constitute the cores of these nanoprobes make them attractive candidates for optical molecular imaging of multiple disease biomarkers. Methods SWIR-emitting rare-earth-doped albumin nanocomposites (ReANCs) were synthesized using controlled coacervation, with visible light-emitting fluorophores additionally incorporated during the crosslinking phase for validation purposes. Specifically, HoANCs, ErANCs, and TmANCs were co-labeled with rhodamine-B, FITC, and Alexa Fluor 647 dyes respectively. These Rh-HoANCs, FITC-ErANCs, and 647-TmANCs were further conjugated with the targeting ligands daidzein, AMD3100, and folic acid respectively. Binding specificities of each nanoprobe to distinct cellular subsets were established by in vitro uptake studies. Quantitative whole-body SWIR imaging of subcutaneous tumor bearing mice was used to validate the in vivo targeting ability of these nanoprobes. Results Each of the three ligand-functionalized nanoprobes showed significantly higher uptake in the targeted cell line compared to untargeted probes. Increased accumulation of tumor-specific nanoprobes was also measured relative to untargeted probes in subcutaneous tumor models of breast (4175 and MCF-7) and ovarian cancer (SKOV3). Preferential accumulation of tumor-specific nanoprobes was also observed in tumors overexpressing targeted biomarkers in mice bearing molecularly-distinct bilateral subcutaneous tumors, as evidenced by significantly higher signal intensities on SWIR imaging. Conclusions The results from this study show that tumors can be detected in vivo using a set of targeted multispectral SWIR-emitting nanoprobes. Significantly, these nanoprobes enabled imaging of biomarkers in mice bearing bilateral tumors with distinct molecular phenotypes. The findings from this study provide a foundation for optical molecular imaging of heterogeneous tumors and for studying the response of these complex lesions to targeted therapy.

(DME)2Ln(SeC6F5)3 (Ln = Nd, Er, Tm) can be isolated in high yield by reductive cleavage of the Se-Se bond in (SeC6F5)2 with elemental Ln in DME. All three Ln compounds are isostructural, with 8 coordinate Ln bound to four O from DME, three terminally bound Se(C6F5), and a dative bond from an arene fluoride to a fluorine at the ortho position of one selenolate. Emission measurements indicate that these compounds are bright NIR sources.

Sodium rare earth fluorides, NaREF4 (RE = rare earth), are used as luminescent materials for light emission and biomedical applications and are important compositions for extracting and separating RE elements. Solution calorimetric measurements of a series of β-structured NaREF4 (Na1.5RE1.5F6) phases with various RE elements determined their heats of formation. Though the lattice contracts from light to heavy RE elements, NaREF4 compounds show more exothermic enthalpies of formation from binary components with the decrease of RE3+ radii, contrary to behavior seen in most RE oxide ternary compounds. By constructing Born–Haber cycles, the different slopes of lines relating lattice energies to lattice parameters in binary and ternary fluorides appear to be the reason for this reverse trend, which can be associated with changes in the coordination number of RE cations. These trends and the metastability of sodium light RE fluorides not only reveal the key role of ionic radius in RE compound stability, but also are significant for the design and synthesis of new materials and motivate the more effective utilization of RE.

Checkpoint immunotherapy, through the reversal of tumor-mediated inactivation of the immune system, has shown promise in the treatment of several types of cancer. This has culminated in the approval of seven immune checkpoint inhibitors (ICIs). However, only a small population of patients respond to these drugs. Because of the physical and economic burden of ICIs on the patient, there is a critical need to identify biomarkers that can inform on the potential response to ICIs. The presence of tumor infiltrating lymphocytes (TILs) has demonstrated good prognostic value in determining if a patient should receive ICIs. Current clinical methods to assess TILs involve invasive biopsies and immunohistochemistry, which suffer from intratumoral heterogeneity, observer variability, and a lack of real-time feedback. Here, we report on near infrared light excitable rare earth metal-based nanoparticles, termed rare earth albumin nanocomposites (ReANCs), that emit shortwave infrared (SWIR) light, allowing for deep tissue imaging and high signal-to-noise ratios compared to visible or near infrared fluorescence probes. Tumor-targeted ReANCs have been previously employed to monitor tumor progression and response to chemotherapy in mouse models of breast cancer metastasis. In this study, to target CD3+ T cells, ReANCs were conjugated using the zero-length cross-linker 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) to a peptide derived from the sequence of the CD3-ϵ receptor sub-unit. Target specific binding was validated by flow cytometry as a measure of increased uptake of peptide-conjugated ReANCs by Jurkat cells. To specifically target cytotoxic T lymphocytes, we employed the fragment antigen binding (Fab) derived from enzymatic digestion of a CD8 antibody (clone 53-6.7) with papain. The Fab fragments were conjugated to ReANCs with sulfo-succinimidyl 4-(N-maleimidomethyl)cyclohexane-1-carboxylate (sulfo-SMCC). Conjugation was confirmed by non-reducing gel electrophoresis and high performance liquid chromatography (HPLC). A loading efficiency of approximately 60% was achieved. Target specific binding was validated by flow cytometry as a measure of increased uptake of Fab-conjugated ReANCs by T cells isolated from splenocytes. We generated a metric for measuring immune burden around tumor spheroids by pre-labeling T cells with ReANCs and co-culturing them with tumor cell spheroids in vitro. Imaging of T cells with CD3 and CD8-targeted ReANCs provides a basis for future in vivo small animal imaging studies where we will investigate the potential of this technology to track immune cells in relation to a tumor in real time. Metrics of immune cell imaging will then inform on the potential of immunotherapy and monitor response to treatment in a longitudinal study. Citation Format: Jay V. Shah, Jake N. Siebert, Amber Gonda, Rahul Pemmaraju, Shashank Kosuri, Carolina Bobadilla Mendez, Xinyu Zhao, Shuqing He, Richard E. Riman, Mei Chee Tan, Mark C. Pierce, Edmund C. Lattime, Prabhas V. Moghe, Vidya Ganapathy. Rare earth albumin nanoparticles engineered to target cytotoxic T cells to evaluate response to immunotherapy [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2021; 2021 Apr 10-15 and May 17-21. Philadelphia (PA): AACR; Cancer Res 2021;81(13_Suppl):Abstract nr 2802.

The identification and molecular profiling of early metastases remains a major challenge in cancer diagnostics and therapy. Most in vivo imaging methods fail to detect small cancerous lesions, a problem that is compounded by the distinct physical and biological barriers associated with different metastatic niches. Here, we show that intravenously injected rare-earth-doped albumin-encapsulated nanoparticles emitting short-wave infrared light (SWIR) can detect targeted metastatic lesions in vivo, allowing for the longitudinal tracking of multi-organ metastases. In a murine model of basal human breast cancer, the nanoprobes enabled whole-body SWIR detection of adrenal gland microlesions and bone lesions that were undetectable via contrast-enhanced magnetic resonance imaging (CE-MRI) as early as, respectively, three weeks and five weeks post-inoculation. Whole-body SWIR imaging of nanoprobes functionalized to differentially target distinct metastatic sites and administered to a biomimetic murine model of human breast cancer resolved multi-organ metastases that showed varied molecular profiles at the lungs, adrenal glands and bones. Real-time surveillance of lesions in multiple organs should facilitate pre-therapy and post-therapy monitoring in preclinical settings.

A model has been developed for calculating thermodynamic properties and phase equilibria in binary and multicomponent aqueous systems containing rare earth element chlorides. Here, the rare earth elements encompass the lanthanides except promethium plus yttrium. The model is based on a comprehensive database of solid-liquid equilibria, osmotic and activity coefficients, enthalpies of dilution and heat capacities of solutions. The computational framework relies on the previously developed Mixed-Solvent Electrolyte (MSE) model. The model accurately reproduces the properties of binary rare earth chloride – water systems and of ternary mixtures that additionally include HCl, NaCl, or CaCl2. Solid-liquid phase diagrams have been obtained to provide a convenient summary of the solubility of stable and metastable hydrated solid phases. Analysis of the stability of solid hydrates reveals systematic trends within the rare earth series. At ambient and elevated temperatures, the calculations show an increase in the stability range of rare earth chloride hexahydrates with decreasing cation radius, accompanied by a gradual disappearance of the heptahydrate. At low temperatures, the stable solid phases transition from the decahydrate at higher cation radii to octahydrate in an intermediate range and a combination of pentadeca- and nonahydrates at lower radii. The calculated standard-state enthalpies of formation of the hydrates agree with independently obtained values from calorimetric measurements, thus verifying the internal consistency of the model.

Bastnasite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnasite, a fundamental understanding of the structure and surface properties of bastnasite is essential. In our earlier work (J. Phys. Chem. C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnasite. In this work, we make a comparative study of the surface properties of Ce-bastnasite, La-bastnasite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnasite than on La-bastnasite. The order of stabilities for stoichiometric surfaces is as follows: [100] > [101] > [102] > [0001] > [112] > [104] and the most favorable adsorption sites for water molecules are the same as for La-bastnasite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Due to similar water adsorption energies on bastnasite [101] and calcite [104] surfaces, the design of collector molecules that selectively bind to bastnasite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.

Rare earth elements (REE) are technology drivers, essential for applications ranging from clean energy technologies to biomedical imaging. Thus they are “critical elements” and it is desirable to find additional RE domestic sources and explore green extraction technologies to overcome their supply risk. Phosphogypsum, a major byproduct of the phosphate fertilizer industry, incorporates a significant amount of RE from the apatite source rock and thus is a potential alternate source of RE. To know the accessibility and extractability of RE from phosphogypsum, it is important to understand the location and nature of RE binding. Here, we report the synthesis of analogs of RE-doped phosphogypsum, with europium (Eu) as a model RE. Using several characterization tools we conclude that the majority of Eu is on the surface of the calcium sulfate crystal as a separate secondary phase, namely a metastable amorphous/nanocrystalline precipitate in which Eu is associated with phosphate and sulfate as counterbalancing ions. The rapid precipitation at low temperature could be responsible for this behavior, which may not represent equilibrium, and our experiments are comparable in the timescale with the fast phosphogypsum precipitation in the industrial process. These results suggest that the Eu is not entrapped by ionic substitutions in the calcium sulfate lattice. Thus RE should be extracted relatively easily from phosphogypsum using methods that extract the RE from its surface.

Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements (REEs) such as Y, La, and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. To design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnasite is essential. Unexpectedly, density functional theory (DFT) calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La-bastnasite is isomorphic to the structure of Ce-bastnasite belonging to the P62c space group, whereas the common structure listed in the Inorganic Crystal Structure Database structure belonging to the P62m space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic La-bastnasite to support these theoretic...

Bastnaesite, [RE-CO 3 -OH/F] (RE = rare earth) is one of the major sources of rare earth elements found in commercial deposits at Mountain Pass, California, Bayan Obo, China, and elsewhere. Synthetic forms of bastnaesite have been explored for applications including optical devices and phosphors. Determination of thermodynamic properties of these phases is critical for understanding their origin, mining, and processing. We report the first experimental determination of formation enthalpies of several OH and F bastnaesites based on high-temperature oxide melt solution calorimetry of well-characterized synthetic samples. The formation enthalpies from binary oxides and fluorides for all the bastnaesite samples are highly exothermic, consistent with their stability in the garnet zone of the Earth’s crust. Fluoride bastnaesite, which is more abundant in nature than its hydroxide counterpart, is thermodynamically more stable. For both OH and F bastnaesite, the enthalpy of formation becomes more negative with increasing ionic radius of the RE 3+ cation. This periodic trend is also observed among rare earth phosphates and several other rare earth ternary oxides. For a given RE, the formation enthalpies from binary oxides are more negative for orthophosphates than for bastnaesites, supporting the argument that monazite could have formed by reaction of bastnaesite and apatite at high temperature. The difference in formation enthalpy of monazite and bastnaesite provides insight into energetics of such reactions along the rare earth series.

A general overview of the trends in structural and thermodynamic properties that have been identified within the hydrated normal rare earth carbonates and the rare earth hydroxycarbonates is presented. Based upon available literature, we demonstrate the trends in crystallographic unit cell parameters, thermal stability, aqueous solubility, and thermochemical properties. These trends can be attributed to both the unique chemistry and strong similarity of the rare earth elements. There are also inconsistent trends that signal research needs to better understand the structure–energy relationships of the rare earth carbonates.

High-refractive-index ZrO2 nanoparticles were used to tailor the refractive index of a polymer matrix to match that of luminescent lanthanide-ion-doped (La0.92Yb0.075Er0.005F3) light-emitting particles, thereby reducing scattering losses to yield highly transparent emissive composites. Photopolymerization of blends of an amine-modified poly(ether acrylate) oligomer and tailored quantities of ZrO2 nanoparticles yielded optically transparent composites with tailored refractive indices between 1.49 and 1.69. By matching the refractive index of the matrix to that of La0.92Yb0.075Er0.005F3, composites with high transmittance (>85%) and low haze from the visible to infrared regions, bright 1530 nm optical emissions were achieved at solids loadings of La0.92Yb0.075Er0.005F3, ranging from 5 to 30 vol %. These optical results suggest that a hybrid matrix approach is a versatile strategy for the fabrication of functional luminescent optical composites of high transparency.

Realizing the promise of precision medicine in cancer therapy depends on identifying and tracking of cancerous growths in order to maximize treatment options and improve patient outcomes. However, this goal of early detection remains unfulfilled by current clinical imaging techniques that fail to detect diseased lesions, due to their small size and sub-organ localization. With proper probes, optical imaging techniques can overcome this limitation by identifying the molecular phenotype of tumors at both macroscopic and microscopic scales. In this study, we propose the first use of nanophotonic short wave infrared technology to molecularly phenotype small sub-surface lesions for more sensitive detection and improved patient outcomes. To this end, we designed human serum albumin encapsulated rare-earth (RE) nanoparticles (ReANCs)[1, 2] with ligands for targeted lesion imaging. AMD3100, an antagonist to CXCR4 (a chemokine receptor involved in cell motility and a classic marker of cancer metastasis) was adsorbed onto ReANCs to form functionalized ReANCs (fReANCs). Functionalized nanoparticles were able to discriminate and preferentially accumulate in receptor positive lesions when injected intraperitoneally in a subcutaneous tumor model. Additionally, fReANCs, administered intravenously, were able to target sub-tissue tumor micro-lesions, at a maximum depth of 10.5 mm, in a lung metastatic model of breast cancer. Internal lesions identified with fReANCs were 2.25 times smaller than those detected with unfunctionalized ReANCs (p < .01) with the smallest tumor being 18.9 mm3. Thus, we present an integrated nanoprobe detection platform that allows target-specific identification of sub-tissue cancerous lesions.

Seasonal and spatial variations of the light absorption coefficient, a(λ), were investigated in the New York/New Jersey Harbor Estuary (i.e., Jamaica Bay, Hudson/Raritan Bay, and Inner Harbor) from August 2008 through June 2009 to characterize the bio-optical characteristics of the estuary. The nonalgal particles (NAP) made a constant light absorption contribution of 18 ± 6% (mean ± standard deviation) (440 nm) over the entire estuary. Covariation among chlorophyll a, total suspended solid, and colored dissolved organic matter (CDOM) was not observed, indicating optical complexity of the estuary. Two optical domains were observed: a phytoplankton-dominated regime (Jamaica Bay) and a CDOM dominated regime (Inner Harbor and Hudson/Raritan Bay). Specific absorption coefficient a ph * (λ) decreased with increasing chlorophyll a; this was due to the large cell sizes of diatoms based on package effect analysis. The sources of CDOM and NAP were terrestrial and of in situ origins, respectively. The slopes of CDOM (S CDOM) and NAP (S NAP) of the estuary were reported for the first time. Overall, this study provided the most complete characterization of light absorption for the New York/New Jersey Harbor Estuary, which will provide critical parameters and insights to build/refine remote sensing models for monitoring water quality in the estuary.

Rare earth elements (RE) are incorporated into a large variety of complex oxide phases to provide tailored mechanical, electrical, optical, and magnetic properties. Thermodynamics control phase stability, materials compatibility in use, corrosion, and transformation. This review presents, in one compilation, the thermodynamic properties of a large number of such materials and discusses systematic trends in energetics and the factors controlling stability.

Rare-earth-doped nanocomposites have appealing optical properties for use as biomedical contrast agents, but few systems exist for imaging these materials. We describe the design and characterization of (i) a preclinical system for whole animal in vivo imaging and (ii) an integrated optical coherence tomography/confocal microscopy system for high-resolution imaging of ex vivo tissues. We demonstrate these systems by administering erbium-doped nanocomposites to a murine model of metastatic breast cancer. Short-wave infrared emissions were detected in vivo and in whole organ imaging ex vivo. Visible upconversion emissions and tissue autofluorescence were imaged in biopsy specimens, alongside optical coherence tomography imaging of tissue microstructure. We anticipate that this work will provide guidance for researchers seeking to image these nanomaterials across a wide range of biological models.

Rare-earth ions are used in a wide range of emissive devices – ranging from lasers to displays – where high optical efficiency and narrow-linewidth are important. While their radiative properties are important, nonradiative properties are also critical since they can reduce optical efficiency and generate heat. In this paper, theories for multiphonon relaxation rate are reviewed for rare-earth excited states in solid-state dielectric hosts. A range of various approaches are used to simplify the mathematical form of the rate equations. The 2H9/2 excited state of Er3+, responsible for a technologically significant green emission, is modeled to show how the various theories manifest an order-of-magnitude variation in the thermal dependence of the multiphonon relaxation rate, as well as anomalous local minima in phonon scattering for temperatures above 0 K. This work proposes a corrective term of two quanta (Δν= + 2) of the mediating phonon energy to energy gap, so the calculated and the experimentally determined relaxation rates are equal. Radiative quantum efficiencies of both the 1G4→3H5 ~1.3 μm and 3F3→3F2 ~7 μm of Pr3+ are calculated to show the importance of both proper measurement of phonon energy and application of the multiphonon relaxation rate theory.

We are investigating the ability of targeted rare earth (RE) doped nanocomposites to detect and track micrometastatic breast cancer lesions to distant sites in pre-clinical in vivo models. Functionalizing RE nanocomposites with AMD3100 promotes targeting to CXCR4, a recognized marker for highly metastatic disease. Mice were inoculated with SCP-28 (CXCR4 positive) and 4175 (CXCR4 negative) cell lines. Whole animal in vivo SWIR fluorescence imaging was performed after bioluminescence imaging confirmed tumor burden in the lungs. Line-scanning confocal fluorescence microscopy provided high-resolution imaging of RE nanocomposite uptake and native tissue autofluorescence in ex vivo lung specimens. Co-registered optical coherence tomography imaging allowed assessment of tissue microarchitecture. In conclusion, multiscale optical molecular imaging can be performed in pre-clinical models of metastatic breast cancer, using targeted RE-doped nanocomposites.

This review surveys the chemistry and extraordinary NIR spectroscopy of molecules and clusters with bonds between Lanthanide ions and the group 16 elements Sulfur and Selenium.

Hydrothermal and commercial barium titanate powders were examined for undesirable impurity phases. Compositional differences in the powder were evaluated using x-ray diffraction (XRD), x-ray fluorescence (XRF), and x-ray photoelectron spectroscopy (XPS). A barium-rich impurity phase, virtually undetectable by XRD, was detected via XPS. Barium impurity phase peaks were detected at binding energies @1.5 eV higher than those characteristic of barium in a barium titanate bonding state for both the Ba 3d and Ba 4d transitions. Simple curve-fitting techniques were used to quantify the percentage of barium in a barium titanate bonding state versus another barium bonding state for each set of doublets. The barium impurity bonding state accounted for 20-50 mol% of the barium detected by XPS.

A method was developed to granulate ceramic particles using metallo-organic soap as a binder. A high shear mechanical mixer (i.e., mechanofusion) was used to coat the soap over the ceramic particle surfaces. Agglomeration of the coated particles was triggered by increasing the mixing temperature to the softening point of the soap and transforming the soap from a crystalline to an amorphous phase. The crystalline soap acted as a solid lubricant and the amorphous phase was a cohesive binder. Granule growth was correlated to the thermomechanical properties of the soap, which depended on temperature, applied pressure and compaction history. The resultant spherical granules were densely packed assemblages of coated particles (i. e., multicore microcapsules). Sequential cladding of layers onto pre-formed core granules resulted in microstructures with hierarchical compositional ordering.

Contrast agents designed to visualize the molecular mechanisms underlying cancer pathogenesis and progression have deepened our understanding of disease complexity and accelerated the development of enhanced drug strategies targeted to specific biochemical pathways. For the next generation probes and imaging systems to be viable, they must exhibit enhanced sensitivity and robust quantitation of morphologic and contrast features, while offering the ability to resolve the disease-specific molecular signatures that may be critical to reconstitute a more comprehensive portrait of pathobiology. This feature article provides an overview on the design and advancements of emerging biomedical optical probes in general and evaluates the promise of rare earth nanoprobes, in particular, for molecular imaging and theranostics. Combined with new breakthroughs in nanoscale probe configurations, and improved dopant compositions, and multimodal infrared optical imaging, rare-earth nanoprobes can be used to address a wide variety of biomedical challenges, including deep tissue imaging, real-time drug delivery tracking and multispectral molecular profiling.

Riman, Richard Eric/0000-0002-4289-5768; Vakifahmetoglu, Cekdar/0000-0003-1222-4362 WOS:000326712200047 Acmite (NaFeSi2O6) films were formed on steel coupons via solvothermal reaction of silica, sodium hydroxide, and 1, 4-butanediol in an autoclave under autogenous pressure. Systematic variation in processing variables led to homogenous coatings comprised of pinacoidal acmite grains with an average grain size of similar to 33m. The coatings were produced on the steel coupons from reactant conditions of 0.635m SiO2, 2.546m NaOH, and 3.087m 1,4-butanediol for 72h at 240 degrees C. DOW Chemical Corporation; PPG Corporation The authors acknowledge Dr. Hebert of Materials Science and Engineering at University of Connecticut for his aid in analyzing the metal-ceramic interface with FIB and EDS techniques. Support for this work was received from DOW Chemical Corporation and PPG Corporation.

Monodisperse β-NaYF4:Yb,Er nanocrystals with mean sizes of 11, 40, and 110 nm were synthesized by a thermal decomposition solvothermal process to better understand the relationship between particle size and optical properties. A systematic study of luminescence intensity versus size revealed that both visible upconversion and infrared downconversion emission intensities decrease with decreasing nanocrystal size. The intrinsic quantum efficiency of the infrared 4I13/2 → 4I15/2 downconversion transition was studied in great detail since this specific transition allows us to quantify the contribution of nonradiative losses more easily than the observed upconversion transitions. The intrinsic quantum efficiency of the 4I13/2→4I15/2 transition decreased from 50% (110 nm) to 15% (11 nm). Multiphonon relaxation and −OH quenching was studied in these materials by measuring the vibrational characteristics of β-NaYF4:Yb,Er nanospheres. While multiphonon relaxation exhibited increased contribution to nonradiative de...

Success of personalized medicine in cancer therapy depends on the ability to identify and molecularly phenotype tumors. Current clinical imaging techniques cannot be integrated with precision molecular medicine at the level of single cells or microlesions due to limited resolution. In this work we use molecularly targeted infrared emitting optical probes to identify and characterize metastatic microlesions prior to their detection with clinically relevant imaging modalities. These contrast agents form the basis of an in vivo optical imaging system capable of resolving internal microlesions, filling a critical unmet need in cancer imaging.

With the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb(3+) could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb(3+) by citrate. No reduction in Tb(3+) adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.

Monoethanolamine (MEA) scrubbing is an energy-intensive process for carbon capture and sequestration (CCS) due to the regeneration of amine in stripping towers at high temperature (100–120°C) and the subsequent pressurization of CO2 for geological sequestration. In this paper, we introduce a novel method, reactive hydrothermal liquid phase densification (rHLPD), which is able to solidify (densify) monolithic materials without using high temperature kilns. Then, we integrate MEA-based CCS processing and mineral carbonation by using rHLPD technology. This integration is designated as rHLPD-carbon sequestration (rHLPD-CS) process. Our results show that the CO2 captured in the MEA-CO2 solution was sequestered by the mineral (wollastonite CaSiO3) carbonation at a low operating temperature (60°C) and simultaneously monolithic materials with a compressive strength of ~121 MPa were formed. This suggests that the use of rHLPD-CS technology eliminates the energy consumed for CO2-MEA stripping and CO2 compression and also sequesters CO2 to form value-added products, which have a potential to be utilized as construction and infrastructure materials. In contrast to the high energy requirements and excessive greenhouse gas emissions from conventional Portland cement manufacturing, our calculations show that the integration of rHLPD and CS technologies provides a low energy alternative to production of traditional ­cementitious-binding materials.

We describe the development and testing of a line-scanning confocal microscope and integrated confocal / optical coherence tomography system for imaging biological cells and tissues labeled with molecularly-targeted rare-earth-doped nanocomposites.

Barium magnesium tantalate Ba(Mg1/3Ta2/3)O3 (BMT) nanopowders were synthesized at a low temperature of 220 °C through glycothermal reaction by using Ba(OH)2·8H2O, Mg(NO3)·6H2O, and TaCl5 as precursors and 1,4-butanediol as solvent. It is demonstrated that higher synthesis temperatures and co-precipitation of magnesium and tantalum improve the incorporation of magnesium into BMT nanopowders under glycothermal treatment and produce a homogeneous, stoichiometric powder. The glycothermally derived BMT nanopowders are very reactive and provide a high-density sintered body with 97.1% of theoretical density at a low temperature of 1350 °C. The average grain size of the sintered ceramics was 1.2 ± 0.2 μm and relatively uniform in comparison with the ceramics sintered with powders produced from the conventional method.

Infrared-to-visible rare earth doped upconversion phosphors that convert multiple photons of lower energy to higher energy photons offer a wide range of technological applications. The brightness (i.e., emission intensities) and energy efficiency of phosphors are important performance characteristics that determine which applications are appropriate. Optical efficiency can be used as a measure of the upconversion emission performance of these rare earth doped phosphors. In this work, hexagonal-phase NaYF(4):Yb-Er was synthesized using the hydrothermal method in the presence of surfactants like trioctylphosphine, polyethylene glycol monooleate, and polyvinylpyrrolidone. The upconversion emission optical efficiencies of NaYF(4):Yb-Er were measured to quantify and evaluate the effects of surface coatings and accurately reflect the brightness and energy efficiency of these phosphors. Polyvinylpyrrolidone-modified NaYF(4):Yb-Er particles were found to be ~5 times more efficient and brighter than the unmodified particles. The difference in efficiency was attributed to reduced reflectance losses at the particle-air interface via refractive index mismatch reduction between the core NaYF(4):Yb-Er particles and air using polyvinylpyrrolidone as a surfactant.