Search

Phosphate (Pi) is crucial for various physiological processes and aquatic environments, which emphasizes the need for a simple, on-site sensor to promptly detect Pi for human health and environmental conservation. In this study, we propose a dual-emission ratiometric fluorescence sensor for highly sensitive and visual Pi detection. The sensor employs samarium ions (Sm 3+ ) as a core component, with cadmium telluride quantum dots (CdTe QDs) and ofloxacin (OFL) serving as signal carriers. The CdTe-Sm(III)-OFL nanoprobe emits a purple fluorescence resulting from the red fluorescence of CdTe QDs and the blue-green fluorescence of OFL. The fluorescence of OFL is quenched by Sm 3+ through fluorescence resonance energy transfer (FRET). Upon Pi interaction, the FRET process is disrupted due to the competitive Pi-Sm 3+ binding, which leads to the fluorescence recovery of OFL while the red fluorescence of CdTe remains steady. This enables the construction of a ratiometric fluorescent sensor for Pi detection, manifesting as a color change from purple to blue. The sensor demonstrated a linear response for Pi detection within the range of 0.1-75 μM, with a low detection limit of 17.0 nM. By utilizing the distinct fluorescence responses of various physiological phosphates and employing chemometrics, this innovative dual-emission sensor accurately distinguishes among different physiological phosphates. Furthermore, a portable lab-on-paper device based on CdTe-Sm(III)-OFL, coupled with a smartphone-integrated mini-device, is developed for swift Pi detection using an ordinary smartphone. Analytical performance validated on environmental and biological samples demonstrates the sensor's excellent robustness and adaptability. This study introduces a pioneering approach to fabricate ratiometric fluorescence sensors and customize portable, cost-effective mini-devices for precise target detection, thus opening avenues for advanced sensing strategies in various applications.

Dimetridazole (DMZ) is commonly used as a veterinary drug, resulting in high emissions and environmental pollution and DMZ residues are carcinogenic, genotoxic, and mutagenic to humans. Therefore, it is essential to construct a fast, sensitive and simple sensor to monitor DMZ. In this study, samarium molybdate nanosheets modified multi-walled carbon nanotube composites (SmM/MWCNT) were synthesized to modify GCE for detecting DMZ. The SmM/MWCNT material was also characterized by various analytical and spectroscopic techniques, such as FE-SEM, HRTEM, FT-IR, Raman spectroscopy, XRD, elemental mapping and XPS, to demonstrate the successful synthesis of the composite. Besides, the electrochemical behavior of SmM/MWCNT/GCE for DMZ was also investigated using CV and DPV, and the modified electrode showed good electrochemical sensing performance for DMZ with a low detection limit (0.08 μM), a wide linear range (0.1∼1000 μM), and excellent selectivity. Finally, the SmM/MWCNT/GCE was successfully applied to detect DMZ in environmental and biological samples, and satisfactory recoveries (95%∼105%) were obtained. To the best of our knowledge, the synthesis of SmM/MWCNT and its application in electrochemical sensors are reported for the first time, which demonstrates that it can provide a new route for real-time monitoring of environmental pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A series of compounds with the general formula RE 1.90 Y 0.10 Zr 2 O 7 (where RE includes Eu, Sm and Y includes La, Sm, Eu) were synthesized using a solid-state reaction method. These compounds were analyzed through differential thermal analysis (DTA), thermogravimetric analysis (TG), X-ray powder diffraction (XRD), and scanning electron microscopy (SEM). Additionally, their dielectric constant, loss tangent, piezoelectric charge constant, and Curie temperature were measured using an LCR meter, d 33 meter, and TG/DTA. X-ray diffraction results indicated that all samples crystallize in a cubic pyrochlore structure. Photoluminescence studies revealed that Eu 3+ ions predominantly contribute to the emission, whether as activators or co-activators. Among the phosphors, Eu 1.90 La 0.10 Zr 2 O 7 exhibited a significantly longer afterglow compared to Sm 1.90 Eu 0.10 Zr 2 O 7 and Eu 1.90 Sm 0.10 Zr 2 O 7 . Conversely, Sm 1.90 Eu 0.10 Zr 2 O 7 demonstrated luminescence intensity that was 20 times greater than that of Eu 1.90 La 0.10 Zr 2 O 7 and Eu 1.90 Sm 0.10 Zr 2 O 7 . Furthermore, all samples with characteristic Eu 3+ emissions also exhibited piezoelectric properties. Curie temperature (T c ) of Eu 1.90 La 0.10 Zr 2 O 7 , Sm 1.90 Eu 0.10 Zr 2 O 7 , and Eu 1.90 Sm 0.10 Zr 2 O 7 are 770°C, 830°C, and 845°C, respectively. Therefore, Sm 3+ ion improves piezoelectric properties and Curie temperature when doping into the Eu 2 Zr 2 O 7 host crystal., (© 2024 The Author(s). Luminescence published by John Wiley & Sons Ltd.)

As one of the fundamental physical quantities, temperature is extremely important in various fields. In order to study the temperature sensing characteristics of dual-emitting center phosphors, Bi 3+ -doped and Bi 3+ /Sm 3+ -doped Sr 2 Ga 2 GeO 7 phosphors were synthesized by high-temperature solid-phase method. Under 312 nm excitation, the Sr 2 Ga 2 GeO 7 :Bi 3+ phosphor exhibits a blue broadband emission corresponding to the 3 P 1  →  1 S 0 transition of Bi 3+ ions. By testing the temperature change spectrum of phosphors, it was found that Bi 3+ exhibited strong thermal sensitivity. However, due to the fact that single ion doped phosphors are easily affected by other factors when applied to the field of temperature sensing, based on the thermal sensitivity of Bi 3+ , Sm 3+ with low temperature sensitivity was selected as the co-doped ion, and it was found that the two ions had different thermal quenching characteristics when the temperature change spectrum was tested. Using the temperature detection method based on the fluorescence intensity ratio (FIR) of the dual emission centers, it was found that the best absolute sensitivity S a was 3.125% K -1 and the maximum relative sensitivity S r was 1.275% K -1 in the range of 303-423 K. These results show that Sr 2 Ga 2 GeO 7 :Bi 3+ /Sm 3+ phosphors have broad application prospects in the field of optical temperature sensing., (© 2024 John Wiley & Sons Ltd.)

The photocatalytic properties of CoFe 2 O 4 nanoparticles were activated by the doping and co-doping of a low level of Y 3+ and Sm 3+ cations. After optimizing the annealing temperature, 900 °C was found to be the optimal temperature for the successful incorporation of Y 3+ and Sm 3+ into the spinel structure. The purity of our samples annealed at 900 °C was confirmed using several characterization methods, including PXRD, SEM, XPS, VSM, FTIR, and Raman spectroscopy. Thus, we were able to increase the photocatalytic degradation of orange G dye from 9.9 to 64.63% for the Sm 3+ -doped sample, 76.42% for the Y 3+ -doped sample, and even 85.81% for the co-doped sample under 60 min of UV-visible light irradiation. The beneficial effect of samarium and yttrium doping and co-doping is attributed to several factors: the first factor is doped and co-doped rare earth impurities induce distortion in the lattice, the larger the ionic radii of dopant element, the highest is the photocatalytic activity; second factor, upon doping and co-doping of rare earth impurities in the structure of CoFe 2 O 4 leads to the creation of donor state level within the band gap, causing the Fermi energy to shift near the conduction band. Third factor, co-doping produced strong interactions, which accelerated photocarrier mobility and transport; lastly, longer electron-holes lifetime. We have provided a detailed study of the structural, vibrational, and optical properties to support our conclusions., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The preparation of highly active, rare earth, non-platinum-based catalysts for hydrogen evolution reactions (HER) in alkaline solutions would be useful in realizing green hydrogen production technology. Perovskite oxides are generally regarded as low-active HER catalysts, owing to their unsuitable hydrogen adsorption and water dissociation. In this article, we report on the synthesis of Li 2 ZrO 3 perovskites substituted with samarium and terbium cations at A-sites for the HER. LSmZrO 3 (LSmZO) and LTbZrO 3 (LTbZO) perovskite oxides are more affordable materials, starting materials in abundance, environmentally friendly due to reduced usage of precious metal and moreover have potential for several sustainable synthesis methods compared to commercial Pt/C. The surface and elemental composition of the prepared materials have been confirmed by X-ray photoelectron spectroscopy (XPS). The morphology and composition analyses of the LSmZO and LTbZO catalysts showed spherical and regular particles, respectively. The electrochemical measurements were used to study the catalytic performance of the prepared catalyst for hydrogen evolution reactions in an alkaline solution. LTbZO generated 2.52 mmol/g/h hydrogen, whereas LSmZO produced 3.34 mmol/g/h hydrogen using chronoamperometry. This was supported by the fact that the HER electrocatalysts exhibited a Tafel slope of less than 120 mV/dec in a 1.0 M alkaline solution. A current density of 10 mA/cm 2 is achieved at a potential of less than 505 mV. The hydrogen production rate of LTbZO was only 58.55%, whereas LSmZO had a higher Faradaic efficiency of 97.65%. The EIS results demonstrated that HER was highly beneficial to both electrocatalysts due to the relatively small charge transfer resistance and higher capacitance values., (© 2024. The Author(s).)

Investigating novel compounds has become necessary due to the need for sophisticated materials in optoelectronic devices and spintronics. Because of their unique properties, magnesium-based spinels MgSm2X4 (X = S and Se) are very promising for these applications. We used the spin-polarized PBEsol for structural properties and the PBEsol functional for mechanical behavior, both using the WIEN2k code. Both compounds' stability in the magnetic and non-magnetic phases was validated by the Birch-Murnaghan equation of state, and their stability in the cubic phase was verified by the Born stability criterion. Their ductile character was shown by the computation of Pugh's ratio and Poisson ratio. Both MgSm2S4 and MgSm2Se4 display metallic behavior in the spin-up channel and semiconducting behavior in the spin-down channel, indicating a half-metallic nature, according to TB-mBJ potential calculations. With total magnetic moments of 20 μB, both materials showed ferromagnetic properties. Samarium ions contributed 5.27 μB for MgSm2S4 and 5.34 μB for MgSm2Se4. Furthermore, we computed optical parameters in the energy range of 0 to 15 eV, such as absorption, extinction coefficient, reflectivity, dielectric function, and refractive index. Our results demonstrate the potential of MgSm2X4 spinels for future technological developments by revealing their prospective optoelectronic and spintronic applications., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Rahman et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

The present work investigates the structural and luminescence behaviour of Dy 3+ -Sm 3+ co-doped glass ceramics obtained through heat treatment of precursor glasses. The growth of SiO 2 polycrystalline particles and evolution of these crystallites in the glass domain are witnessed via XRD and FESEM study. The presence of network vibrational bands, hydroxyl groups and the increased quantity of bridging oxygens (BOs) in glass ceramics are analysed through FTIR spectroscopy study. The absorption study (UV-Visible-NIR) showed the possible electronic transitions of Dy 3+ and Sm 3+ ions. The red shift in the absorption band edges and the lower bandgap values are obtained as a result of improved heat treatment in glass ceramics. Emission studies show the enhanced luminescence intensity of glass ceramics under 350 and 402 nm excitations. Decay measurement of glass ceramics showed the improved lifetimes of Dy 3+ and Sm 3+ ions to have appeared in microseconds (×10 -6  s). The colour characteristics of glass ceramics analysed using CIE colour chromaticity diagram and correlated colour temperature (CCT) values suggest the neutral to cool white light emissions. Therefore, prepared glass ceramics with SiO 2 polycrystalline phase are considered to be suitable materials in cool white LEDs applications., (© 2024 The Author(s). Luminescence published by John Wiley & Sons Ltd.)

The abuse and uncontrolled discharge of antibiotics present a severe threat to environment and human health, necessitating the development of efficient and sustainable treatment technology. In this work, we employ a facile one-step electrodeposition method to prepare polyaniline/graphite oxide (PANI/GO) and samarium (Sm) co-modified Ti/PbO 2 (Ti/PbO 2 -PANI/GO-Sm) electrode for the degradation of amoxicillin (AMX). Compared with traditional Ti/PbO 2 electrode, Ti/PbO 2 -PANI/GO-Sm electrode exhibits more excellent oxygen evolution potential (2.63 V) and longer service life (56 h). In degradation experiment, under optimized conditions (50 mg L -1 AMX, 20 mA cm -2 , pH 3, 0.050 M Na 2 SO 4 , 25 °C), Ti/PbO 2 -PANI/GO-Sm electrode achieves remarkable removal efficiencies of 88.76% for AMX and 79.92% for chemical oxygen demand at 90 min. In addition, trapping experiment confirms that ·OH plays a major role in the degradation process. Based on theoretical calculation and liquid chromatography-mass spectrometer results, the heterocyclic portion of AMX molecule is more susceptible to ·OH attacks. Thus, this novel electrode offers a sustainable and efficient solution to address environmental challenges posed by antibiotic-contaminated wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Four eight-coordinated luminescent samarium complexes of type [Sm(hfpd) 3 L 2 ] and [Sm(hfpd) 3 L'] [where hfpd = 1,1,1,5,5,5-Hexafluoro-2,4-pentanedione L = tri-octyl-phosphine oxide (TOPO) and L' = 1,10-phenanthroline (phen), neocuproine (neoc) and bathocuproine (bathoc) were synthesized via a stoichiometrically controlled approach. This allows for precise control over the stoichiometry of the complexes, leading to reproducible properties. This investigation focuses on understanding the impact of secondary ligands on the luminescent properties of these complexes. Infrared (IR) spectra provided information about the molecular structures, whereas 1 H and 13 C nuclear magnetic resonance (NMR) spectra confirmed these structural details along with the coordination of ligands to trivalent Sm ion. The UV-vis spectra revealed the molar absorption coefficient and absorption bands associated with the hfpd ligand and photoluminescence (PL) spectroscopy demonstrated intense orange-red emission (648 nm relative to 4 G 5/2  →  6 H 9/2 ) from the complexes. The Commission Internationale de l'Éclairage (CIE) triangles indicated that the complexes emitted warm orange red light with color coordinates (x, y) ranging from (0.62, 0.36) to (0.40, 0.27). The investigation of the band gap as well as color parameters confirms the utility of these complexes in displays and LEDs., (© 2024 John Wiley & Sons Ltd.)

The present study reports the preparation of crystalline and nanosized copper ferrite (CuFe 2 O 4 ) , Y 3+ substituted CuFe 2 O 4 (CuFe 1.95 Y 0.05 O 4 ), and Sm 3+ substituted CuFe 2 O 4 (CuFe 1.95 Sm 0.05 O 4 ) using a simple co-precipitation method. The XRD analysis confirmed the formation of the cubic spinel phase, while XPS studies validated the presence of Cu and Fe in 2+ and 3+ oxidation states respectively. Transmission electron microscopy (TEM) analysis revealed the nanoparticles with a diameter in the range of 10-60 nm. The introduction of fractional amounts of Y 3+ and Sm 3+ ions in the CuFe 2 O 4 lattice enhanced the reduction of 4-nitrophenol, attributed to decreased particle size facilitating the reduction process. In the case of antimicrobial activity, Candida albican was found to be maximally sensitive to CuFe 2 O 4 and CuFe 1.95 Y 0.05 O 4 , while Pseudomonas aeruginosa was inhibited by CuFe 1.95 Sm 0 . 05 O 4. Moreover, a maximum of 61.9 ± 1.91 % anti-Pseudomonas biofilm activity and 75.7 ± 1.28 % DPPH radical scavenging activity was observed for CuFe 1.95 Y 0.05 O 4 at 200 μg/ml concentration. The improvement in biological activities was attributed to the reduced particle size, crystal structure modification, and increased stability of the CuFe 2 O 4 lattice with substitution. The enhancement in catalytic and biological performance highlighted the effectiveness of minimal Y 3+ and Sm 3+ concentrations in modulating the properties of CuFe 2 O 4 nanomaterials., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Ultra-high thermally stable Ca 2 MgWO 6 :xSm 3+ (x = 0.5, 0.75, 1, 1.25, and 1.5 mol%) double perovskite phosphors were synthesized through solid-state reaction method. Product formation was confirmed by comparing the X-ray diffraction (XRD) patterns of the phosphors with the standard reference file. The structural, morphological, thermal, and optical properties of the prepared phosphor were examined in detail using XRD, Fourier transform infrared spectra, scanning electron microscopy, diffused reflectance spectra, thermogravimetric analysis (TGA), photoluminescence emission, and temperature-dependent PLE (TDPL). It was seen that the phosphor exhibited emission in the reddish region for the near-ultraviolet excitation with moderate Colour Rendering Index values and high colour purity. The optimized phosphor (x = 1.25 mol%) was found to possess a direct optical band gap of 3.31 eV. TGA studies showed the astonishing thermal stability of the optimized phosphor. Additionally, near-zero thermal quenching was seen in TDPL due to elevated phonon-assisted radiative transition. Furthermore, the anti-Stokes and Stokes emission peaks were found to be sensitive toward the temperature change and followed a Boltzmann-type distribution. All these marked properties will make the prepared phosphors a suitable candidate for multifield applications and a fascinating material for further development., (© 2024 John Wiley & Sons Ltd.)

Internal radiotherapy delivers radioactive sources inside the body, near to or into malignant tumours, which may be particularly effective when malignancies are not responding to external beam radiotherapy. A pure beta emitter, 90 Y, is currently used for internal radiotherapy. However, theranostic radionuclide-doped microspheres can be developed by incorporating 153 Sm, which emits therapeutic beta and diagnostic gamma energies. This study investigated the production of high concentrations of samarium-content doped phosphate-based glass microspheres. The glass P60 (i.e. 60P 2 O 5 -25CaO-15Na 2 O) was mixed with Sm 2 O 3 at ratios of 75:25 (G75:Sm25), 50:50 (G50:Sm50) and 25:75 (G25:Sm75) and processed via flame spheroidisation. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) confirmed the microsphere uniformity with significantly high samarium content up to 44 % in G25:Sm75. Via X-ray diffraction (XRD) analysis, samarium-doped microspheres appeared to be glass-ceramic in nature. Mass-loss, size and pH changes were performed over 28 days, revealing a significant increase in samarium microsphere stability. After 15 min of neutron activation (neutron flux 3.01 × 10 13  n.cm -2 .s -1 ), the specific activity of the microspheres (G75:Sm25, G50:Sm50 and G25:Sm75) was 0.28, 0.54 and 0.58 GBq.g -1 , respectively. Therefore, the samarium microspheres produced in this study provide great potential for improving internal radiotherapy treatment for liver cancer by avoiding complex procedures and using less microspheres with shorter irradiation time., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this study, the melt quenching approach is used to synthesize a lead borate-strontium-based glass system doped with samarium ions. Modifications in the glass network structure arising from the addition of various concentrations of Sm 3+ ions were investigated via Fourier transform infrared (FTIR) spectroscopy. FTIR analysis revealed B-O-B bridges, BO 3 , and BO 4 units are present. UV-vis-NIR spectroscopic measurement was performed to study the optical absorption spectra. Optical constants such as optical bandgap energies, refractive indices, and other related parameters were evaluated. The lifetime fluorescence decay was measured and ranged between 1.04 and 1.88 ns. The photoluminescence spectra in the range 500-750 nm revealed four transitions from the ground state 6 G 5/2 to the excited states 6 H 5/2 , 6 H 7/2 , 6 H 9/2 and 6 H 11/2 and J-O theory was utilized to study these optical transitions for Sm 3+ ions. Calculations of the oscillator strengths and J-O intensity parameters were performed and the obtained J-O parameters followed the sequence Ω 4  > Ω 6  > Ω 2 . The ratio O/R indicated a high lattice asymmetry around the samarium ions. The values of lifetimes and branching ratios for the fabricated samples emphasized their suitability to be used in laser applications. The current glass samples are good candidates for orange and red emission devices., (© 2024 John Wiley & Sons Ltd.)

The rare earth metal, samarium (Sm 3+ ) doped bismuth tungstate (Bi 2 WO 6 ) nanoparticles were prepared by a one-pot hydrothermal method. The powder X-ray diffraction (XRD) analysis confirmed the formation of Bi 2 WO 6 with an orthorhombic crystal structure. The crystallite size of Bi 2 WO 6 decreased from 20.73 to 9.25 nm as the Sm substitution in the W lattice increased. The vibrational modes of W-O, Bi-O, and Sm-O were identified in the range of 500-900 cm -1 . The optical bandgap of Sm 3+ doped Bi 2 WO 6 nanoparticles increased from 2.86 to 2.95 eV with higher Sm doping levels. The surface morphology revealed the formation of flower-like sheets in the Sm 3+ doped bismuth tungstate. The energy dispersive X-ray (EDX) spectrum of Sm 3+ doped Bi 2 WO 6 nanoparticles confirmed the presence of Sm, Bi, W, and O without any other impurities. The small peak detected at 1082.14 eV in the survey scan of Sm 3+ doped Bi 2 WO 6 nanoparticles belonged to Sm3d. In the photocatalytic degradation of direct blue 15 (DB15) under visible light irradiation, the efficiency of the nanoparticles increased with higher Sm 3+ concentration. The obtained results demonstrated that the Sm-Bi 2 WO 6 nanosheets could provide an effective and sustainable solution for treating the wastewater containing direct blue 15 dye., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Lower alcohols (C1-C7) have a close relationship with our lives and some of them are harmful to our body's health. For example, liquor mixed with a tiny amount of methanol is harmful to our health. Much of this study is about identifying one or two low-level alcohols. How to detect low-level alcohol and high-throughput and distinguish between analogues of alcohol remains a tremendous challenge. In this study, a new large ring Schiff base Sm(III) complex (Sm-2r) is synthesized with a double emission matrix using the template method. Its dynamic imine bond (CN) and organic ligands (H 2 L2 r ) with molecular rotor properties can respond to changes in viscosity and polarity in external environments. The PCA method is used to turn the data matrix into a fingerprint spectrum to distinguish different alcohols (C1-C7). Sm-2r enables the quantization of cyclopropyl and glycerol. Linear ranges of cyclopropanol and glycerol are 0-9.0% and 0-3.0% (v/v), respectively. In addition, Sm-2r has an excellent ability to distinguish the mixtures of n -PrOH and i-PrOH, C 5 H 9 OH and C 6 H 11 OH, n -PeOH and n -HeOH, 1,3-PDO and 1,2-PDO, MeOH and EtOH, 1,2-EG and 1,2-PDO at different volume ratios. We have provided a way to distinguish alcohol species based on their molecular polarity and viscosity.

Quinolinic acid (QA) is an index for some diseases, whose detection is of importance. This work presents a samarium metal-organic framework (Sm-MOF) containing 5-sulfoisophthalate ligand (SIP 3- ). The fluorescence of Sm-MOF integrates the emission at 339 nm from the SIP 3- ligand and four characteristic 4 G 5/2 → 4 H j ( j = 5/2, 7/2, 9/2, and 11/2) transitions at 559, 596, 642, and 701 nm from Sm(III). Sm-MOF as a turn-off fluorescence sensor to QA exhibits high sensitivity, selectivity, and durability. The fluorescence quenching response to QA shows a linear relationship of I 0 / I = 0.00496· C QA + 1.12474 in the QA concentration of 0-500 μM and a limit of detection calculated as 4.11 μM. Sm-MOF shows the structural and fluorescent stabilities in five quenching-recovery cycles. The recoveries of close to 100% in human urine and serum indicate high reliability. The paper-based Sm-MOF sensor displays a rough QA quantitative analysis by recognizing red values in the on-site QA detection.

Samarium diiodide is a versatile single electron transfer (SET) agent with various applications in organic chemistry. Lewis structures regularly insinuate the existence of a ketyl radical when samarium diiodide binds a carbonyl group. The study presented here investigates this electron transfer by the means of computational chemistry. All electron CASPT2 calculations with the inclusion of scalar relativistic effects predict an endotherm electron transfer from samarium diiodide to acetone. Energies calculated with the PBE0-D3(BJ) functional and a small core pseudopotential are in good agreement with CASPT2. The calculations confirm the experimentally measured increase of the samarium diiodide reduction potential through the addition of hexamethylphosphoramide also known as HMPA.

Production cross sections of 153,145 Sm via alpha-particle-induced reactions on nat Nd were measured up to 23 MeV. The stacked-foil activation technique and high-resolution gamma-ray spectrometry were adopted for the measurement. The obtained cross sections were compared with the literature data and the TENDL-2019 and TENDL-2021 values. Physical thick target yields of the two radionuclides were derived from the measured cross sections., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Strategies for synthesizing polyhydroxylated piperidines such as iminosugars have received broad attention. These substances are known to interact with carbohydrate related enzymes, glycosidases and glycosyltransferases, to which also the large enzyme families of chitin synthases and cellulose synthases belong. Many chemical and biological aspects of chitin synthases remain unexplored due to the fact that modulating substances are hardly available or expensive. Starting from enantiopure D- and L-amino acids, a series of iminosugars was prepared by a Lewis acid-catalyzed cyclization of amino acid-derived unsaturated aldehydes as key step. Therefore, different Lewis acids were tested. For samarium diiodide we observed a superior stereoselectivity in comparison to iron(III) chloride and methylaluminium dichloride. To increase water solubility for testing and measurement of enzyme activity, the cyclization products were further functionalized. We established a novel biological chitin synthesis test system which allows quantitative investigation of chitin synthesis in the chitin fiber producing diatom algae Thalassiosira in vivo under the light microscope. None of the compounds displayed cytotoxicity, but two of the four iminosugars increased the length of the chitin fibers produced. This is a strong indicator that these compounds mimic carbohydrates responsible for restarting chitin polymerization.

Reductive cyclizations of carbonyl compounds, mediated by samarium(II) diiodide (SmI 2 , Kagan's reagent), represent an invaluable platform to generate molecular complexity in a stereocontrolled manner. In addition to classical ketone and aldehyde substrates, recent advances in radical chemistry allow the cyclization of lactone and lactam-type substrates using SmI 2 . In contrast, acyclic esters are considered to be unreactive to SmI 2 and their participation in reductive cyclizations is unprecedented. Here, we report a diastereoselective radical 1,4-ester migration process, mediated by SmI 2 , that delivers stereodefined alkene hydrocarboxylation products via radical cyclization of acyclic ester groups in α-carbomethoxy δ-lactones. Isotopic labeling experiments and computational studies have been used to probe the mechanism of the migration. We propose that a switch in conformation redirects single electron transfer from SmI 2 to the acyclic ester group, rather than the "more reactive" lactone carbonyl. Our study paves the way for the use of elusive ketyl radicals, derived from acyclic esters, in SmI 2 -mediated reductive cyclizations.

Purpose: Hepatic radioembolization is an effective minimally invasive treatment for primary and metastatic liver cancers. Yttrium-90 [90Y]-labelled resin or glass beads are typically used as the radioembolic agent for this treatment; however, these are not readily available in many countries. In this study, novel samarium-153 oxide-loaded polystyrene ([153Sm]Sm2O3-PS) microspheres were developed as a potential alternative to 90Y microspheres for hepatic radioembolization., Methods: The [152Sm]Sm2O3-PS microspheres were synthesized using solid-in-oil-in-water solvent evaporation. The microspheres underwent neutron activation using a 1 MW open-pool research reactor to produce radioactive [153Sm]Sm2O3-PS microspheres via 152Sm(n,γ)153Sm reaction. Physicochemical characterization, gamma spectroscopy and in-vitro radionuclide retention efficiency were carried out to evaluate the properties and stability of the microspheres before and after neutron activation., Results: The [153Sm]Sm2O3-PS microspheres achieved specific activity of 5.04 ± 0.52 GBq·g-1 after a 6 h neutron activation. Scanning electron microscopy and particle size analysis showed that the microspheres remained spherical with an average diameter of ~33 μm before and after neutron activation. No long half-life radionuclide and elemental impurities were found in the samples. The radionuclide retention efficiencies of the [153Sm]Sm2O3-PS microspheres at 550 h were 99.64 ± 0.07 and 98.76 ± 1.10% when tested in saline solution and human blood plasma, respectively., Conclusions: A neutron-activated [153Sm]Sm2O3-PS microsphere formulation was successfully developed for potential application as a theranostic agent for liver radioembolization. The microspheres achieved suitable physical properties for radioembolization and demonstrated high radionuclide retention efficiency in saline solution and human blood plasma., (Copyright © 2022 Wolters Kluwer Health, Inc. All rights reserved.)

Six crimson samarium (III) complexes based on β-ketone carboxylic acid and ancillary ligands were synthesized by adopting the grinding technique. All synthesized complexes were investigated via elemental analysis, infrared, UV-Vis, NMR, TG/DTG and photoluminescence studies. Optical properties of these photostimulated samarium (III) complexes exhibit reddish-orange luminescence due to 4 G 5/2  →  6 H 7/2 electronic transition at 606 nm of samarium (III) ions. Further, energy bandgap, color purity, CIE color coordinates, CCT and quantum yield of all complexes were determined accurately. Replacement of water molecules by ancillary ligands enriched these complexes (S2-S6) with decay time, quantum yield, luminescence, energy bandgap and biological properties than parent complex (S1). Interestingly, these efficient properties of complexes may find their applications in optoelectronics and lighting systems. In addition to these, the antioxidant and antimicrobial assays were also investigated to explore the applications in biological assays., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Trivalent europium-based monochromatic red light-emitting phosphors are an essential component to realize high-performance smart lighting devices; however, the concentration and thermal quenching restrict their usage. Here, we report a series of efficient Eu 3+ -substituted Li 3 Y 3 BaSr(MoO 4 ) 8 red-emitting phosphors based on a stratified scheelite structure with negligible concentration and thermal quenching. All of the host and phosphor compositions crystallize in monoclinic crystal structure (space group C 2/ c ). All of the phosphor compositions produce narrow-band red emission (FWHM ∼6 nm), which is highly apparent to the human eyes, and lead to exceptional chromatic saturation of the red spectral window. Concurrently, detailed investigations were carried out to comprehend the concentration and thermal quenching mechanism. Absolute quantum yields as high as 88.5% were obtained for Li 3 Y 0.3 Eu 2.7 BaSr(MoO 4 ) 8 phosphor with virtuous thermal stability (at 400 K, retaining 87% of its emission intensity). The light-emitting diodes were constructed by coupling Li 3 BaSrY 0.3 Eu 2.7 (MoO 4 ) 8 red phosphor with a near-UV LED chip (395 nm) operated at 20 mA forward bias, and the hybrid white LED (an organic yellow dye + red Li 3 Y 3 BaSr(MoO 4 ) 8 :Eu 3+ phosphor integrated with an NUV LED chip) showed a low CCT (6645 K), high CRI (83) values, and CIE values of x = 0.303; y = 0.368, which indicated that the synthesized phosphors can be a suitable red component for white LEDs. In addition, we have systematically investigated the Sm 3+ and Sm 3+ , Eu 3+ activation in Li 3 Y 3 BaSr(MoO 4 ) 8 to display the latent use of the system in plant growth applications and establish that the phosphor exhibits orange red emission with an intense deep-red emission (645 nm ( 4 G 5/2 → 6 H 9/2 )). The phytochrome (Pr) absorption spectrum well matched the fabricated deep-red LED (by integrating a NUV LED + Li 3 Y 3 BaSr(MoO 4 ) 8 :Sm 3+ and Eu 3+ phosphor) spectral lines.

Pure and varying weigh ratio of Sm 2 O 3 -TiO 2 modified polyaniline nanocomposite has been successfully synthesized using in situ polymerization of aniline solution with Sm 2 O 3 -TiO 2 binary oxide. The nanocomposite have been characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), X-photoelectron microscopy (XPS), Field emission-scanning electron microscope (FE-SEM), transmission electron microscopy (TEM) thermogravimetric analysis (TGA) and LCR meter. The XRD results show synthesis anatase TiO 2 phase with tetragonal structure and (monoclinic and cubic) mixture structure of Sm 2 O 3 . The FE-SEM and TEM measurements appear preparing spherical nanoparticles that covered fiber morphology of polyaniline and successfully in situ polymerization process. The TGA measurements are obtain high thermal stability for polyaniline after incorporation by Sm 2 O 3 -TiO 2 binary oxide nanoparticles. LCR measurement is obtained that the DC conductivity, dielectric constant and dielectric loss of nanocomposite is larger than pure polyaniline and the electric properties increase with increasing the concentration of nanoparticles.

Samarium diiodide (SmI 2 )-mediated desymmetrization of a meso-cyclic 1,3-dione pinacol coupling is described. The reaction proceeds with high stereoselectivity to provide fused carbocyclic compounds with three contiguous stereogenic centers featuring an all-carbon quaternary center and a cis-1,2-diol moiety.

We report photoluminescence and photoionization properties of Sm 2+ ions generated by X-irradiation of nanocrystalline CaF 2 :Sm 3+ prepared by coprecipitation. The nanocrystals were of 46 nm average crystallite size with a distribution of ±20 nm and they were characterised by XRD, TEM and SEM-EDS. At room temperature, the X-irradiated sample displayed broad electric dipole allowed Sm 2+ 4f 5 5d (A 1u ) → 4f 6 7 F 1 (T 1g ) luminescence at 725 nm that narrowed to an intense peak at 708 nm on cooling to ∼30 K. The narrow f-f transitions of Sm 3+ were also observed. The X-irradiation-induced reduction of Sm 3+ + e - → Sm 2+ as a function of X-ray dose was investigated over a very wide dynamic range from 0.01 mGy to 850 Gy by monitoring the photoluminescence intensities of both Sm 2+ and Sm 3+ ions. The reverse Sm 2+ → Sm 3+ + e - photoionization can be modelled by employing dispersive first-order kinetics and using a standard gamma distribution function, yielding an average separation of 13 Å between the Sm 2+ ions and the hole traps ( e.g. oxide ion impurities). The present results point towards potential applications of Sm doped CaF 2 nanocrystals in the fields of dosimetry and X-ray imaging.

Currently, atherosclerosis accounts for the majority of cardiovascular morbidity and mortality worldwide, and predicting the stability of atherosclerotic plaque is the main method to prevent atherosclerotic death. This study aims to establish a dual-label time-resolved fluorescence immunoassay (TRFIA) of matrix metalloprotein-9 (MMP-9) and lipoprotein-associated phospholipaseA2 (Lp-PLA2) to predict atherosclerotic plaque stability. A dual-label TRFIA was introduced for the simultaneous quantification of MMP-9 and Lp-PLA2 using fluorescent lanthanide (Eu 3+ and Sm 3+ ) chelates. The performance (sensitivity, specificity, accuracy, precision and reference intervals in different subjects) of this TRFIA was evaluated and compared with commercial kit. The sensitivity of the TRFIA for MMP-9 was 0.85 ng/mL and for Lp-PLA2 was 0.68 ng/mL with high affinity and specificity. The average recoveries were 94.58% to 109.82%, and 104.32% to 109.26%, respectively. All intra- and inter-assay CVs ranged from 3.10% to 5.46%. For the normal subjects, the cutoff value was 160.70 ng/mL for MMP-9 and 183.73 ng/mL for LP-PLA2; for the subjects with stable plaque, the cutoff value was 181.98~309.22 ng/mL for MMP-9 and 194.73~337.89 ng/mL for LP-PLA2; for the subjects with unstable plaque, the cutoff value was 330.43 ng/mL for MMP-9 and 343.23 ng/mL for LP-PLA2. This TRFIA detection results agreed well with the results of commercial kit (R 2 =0.9567 and R 2 =0.9771, respectively) in clinical serum samples. The TRFIA developed has a wide detection range and good sensitivity for the high-throughput simultaneous detection of MMP-9 and Lp-PLA2 in serum, which provides a new method for predicting the stability of atherosclerotic plaque., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

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

Facile electron transport and intimate electronic contact at the catalyst-electrode interface are critical for the ideal performance of electrochemical devices such as glucose biofuel cells and biosensors. Here, through a comprehensive experimental-theoretical exploration, we demonstrate that engineering of interfacial properties, including interfacial electron dynamics, electron affinity, electrode-catalyst-adsorbate electrical synergy, and electrocatalytically active surface area, can lead to highly efficient graphene-based electrochemical devices. We selected two closely related but electronically and surface chemically different functionalized graphene analogues-graphene acid (GA) and reduced graphene oxide (rGO)-as the model graphenic platforms. Our studies reveal that compared to rGO, GA is a superior bifunctional catalyst with high oxygen reduction reaction (an onset potential of 0.8 V) and good glucose oxidation activities. Spectroscopic and electrochemical analysis of GA and rGO indicated that the higher carboxylic acid content on GA increases its overall electron affinity and coupled with improved conductivity and band alignment, which leads to GA's better electrochemical performance. The formulation of a heterostructure between GA and samarium oxide (Sm 2 O 3 ) nanoparticles led to augmented conductivity (lower charge-transfer resistance) and glucose binding affinity, resulting in a further enhanced glucose oxidation activity. The interdimensional Sm 2 O 3 /GA heterostructure, leveraging their enhanced glucose oxidation capacity, exhibited excellent nonenzymatic amperometric glucose sensing performance, with a detection limit of 107 nM and a sensitivity of 20.8 μA/μM. Further, a nonenzymatic, membrane-free glucose biofuel cell (with Sm 2 O 3 /GA heterostructure as anode and GA as biocathode) produced a power density of 3.2 μW·cm -2 (in PBS spiked with 3 mM glucose), which can function as self-powered glucose sensors with 70 nM limit of detection. The study establishes the potential of interfacial engineering of GA to engage it as a highly tunable substrate for a broad range of electrochemical applications, especially in future self-powered biosensors.

An efficient and simple approach for stereoselective synthesis of β-Kdo C -glycosides was described, which relies on easily available peracetylated anomeric acetate or anomeric 2-pyridyl sulfide to couple with carbonyl compounds via SmI 2 -mediated Reformatsky reactions. The utility of this methodology is exemplified by the streamlined synthesis of a practical β-Kdo C -glycoside with an anomeric aminopropyl linker to conjugate with other biomolecules for further biological studies.

TiO 2 nanopowders modified by Nd and Sm were prepared using the sol-gel technique. It was found by XRD analysis that the samples containing Sm are amorphous up to 300 °C, while those with Nd preserve a mixed organic-inorganic amorphous structure at higher temperatures (400 °C). The TiO 2 (rutile) was not detected up to 700 °C in the presence of both modified oxides. TiO 2 (anatase) crystals found at about 400 °C in the Sm-modified sample exhibited an average crystallite size of about 25-30 nm, while doping with Nd resulted in particles of a lower size-5-10 nm. It was established by DTA that organic decomposition is accompanied by significant weight loss occurring in the temperature range 240-350 °C. Photocatalytic tests showed that the samples heated at 500 °C possess photocatalytic activity under UV irradiation toward Malachite green organic dye. Selected compositions exhibited good antimicrobial activity against E. coli K12 and B. subtilis .

Purpose: Nanoparticles (NPs) with radioactive atoms incorporated within the structure of the NP or bound to its surface, functionalized with biomolecules are reported as an alternative to low-dose-rate seed-based brachytherapy. In this study, authors report a mathematical dosimetric study on low-dose rate brachytherapy using radioactive NPs., Method: Single-cell dosimetry was performed by calculating cellular S-values for spherical cell model using Au-198, Pd-103 and Sm-153 NPs. The cell survival and tumor volume versus time curves were calculated and compared to the experimental studies on radiotherapeutic efficiency of radioactive NPs published in the literature. Finally, the radiotherapeutic efficiency of Au-198, Pd-103 and Sm-153 NPs was tested for variable: administered radioactivity, tumor volume and tumor cell type., Result: At the cellular level Sm-153 presented the highest S-value, followed by Pd-103 and Au-198. The calculated cell survival and tumor volume curves match very well with the published experimental results. It was found that Au-198 and Sm-153 can effectively treat highly aggressive, large tumor volumes with low radioactivity., Conclusion: The accurate knowledge of uptake rate, washout rate of NPs, radio-sensitivity and tumor repopulation rate is important for the calculation of cell survival curves. Self-absorption of emitted radiation and dose enhancement due to AuNPs must be considered in the calculations. Selection of radionuclide for radioactive NP must consider size of tumor, repopulation rate and radiosensitivity of tumor cells. Au-198 NPs functionalized with Mangiferin are a suitable choice for treating large, radioresistant and rapidly growing tumors.

Introduction: Radiosynovectomy (RS) with 90 Y-hydroxyapatite ( 90 Y-HyA) aims to control knee hemarthrosis in hemophiliac patients to prevent secondary arthropathy. However, knee RS using 153 Sm-hydroxyapatite ( 153 Sm-HyA) is considered less suitable due to the lower average soft tissue range and energy of 153 Sm for large joints, such as the knees., Purpose: The objective of this investigation was to assess the efficacy and safety of knee RS with 153 Sm-HyA, compared to 90 Y-HyA., Methods: Forty patients were prospectively assigned to undergo knee RS with 153 Sm-HyA (n = 19) or with 90 Y-HyA (n = 21). The frequency of hemarthrosis episodes before and after treatment were compared., Results: After six months of knee RS, 153 Sm-HyA and 90 Y-HyA promoted a similar reduction of hemarthrosis episodes (50% and 66.7%, respectively). However, after 12 months of knee RS, the reduction of hemarthrosis episodes was significantly (p = 0.037) higher using 153 Sm-HyA (87.5%) compared to 90 Y-HyA (50.0%). This discrepancy was more pronounced (p = 0.002) for 153 Sm-HyA compared to 90 Y-HyA in adults/adolescents., Conclusion: Knee radiosynovectomy with 153 Sm-HyA is safe, reduces hemarthrosis episodes after 12 months of treatments, especially in adults/adolescents and even with grades III/IV arthropathy, similar to 90 Y-HyA. 90 Y-HyA seems to promote better hemarthrosis control in small children.

This work furthers the development of counter-current chromatography as an industrial separation process method. It was demonstrated that the industrial counter-current chromatography methods, in particular, for the separation groups of rare earth metals, can be implemented in a modified cascade of centrifugal mixer-settler extractors. The retention behavior of rare earth elements (samarium, europium, gadolinium, terbium, dysprosium and yttrium) on the pilot chromatographic unit consisting of 70 serially connected centrifugal mixer-settler extractors was experimentally studied under isocratic elution conditions using the mixture of 30 vol.% Cyanex Ⓡ 572 + 10 vol.% tributylphosphate in a hydrocarbon diluent as the stationary phase and aqueous nitric acid as the mobile phase. Theoretical analysis of experimental studies showed an acceptable agreement between the assumptions of the theory and experimental results., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Nanothermometry is the study of temperature at the submicron scale with a broad range of potential applications, such as cellular studies or electronics. Molecular luminescent-based nanothermometers offer a non-contact means to record these temperatures with high spatial resolution and thermal sensitivity. A luminescent-based molecular thermometer comprised of visible-emitting Ga 3+ /Tb 3+ and Ga 3+ /Sm 3+ metallacrowns (MCs) achieved remarkable relative thermal sensitivity associated with very low temperature uncertainty of S r =1.9 % K -1 and δT<0.045 K, respectively, at 328 K, as an aqueous suspension of polystyrene nanobeads loaded with the corresponding MCs. To date, they are the ratiometric molecular nanothermometers offering the highest level of sensitivity in the physiologically relevant temperature range., (© 2020 Wiley-VCH GmbH.)

A pathogenic bacterium has its own mechanisms for not only pathogenic attack but also exogenous invasion defense, in which the bacterial cell wall is the front line of attack and defense. We developed a biochemical lanthanide-encoding approach to quantify the uncanonical d-amino acid (d-X) that was edited in a small proportion into the terminal acyl-d-Ala-d-X of nascent peptidoglycan UDP-MurNAc-pentapeptides in the bacterial cell wall. This approach overcomes the difficulties regarding quantification and accuracy issues encountered by the popular optical imaging and traditional high-performance liquid chromatography-based methods. Newly synthesized azide -d-Leu and ketone -d-Met were used together with alkynyl -d-Ala for their metabolic assembly and then bioorthogonally encoded by the correspondingly fabricated DBCO -DOTA-Gd, H 2 NO -DOTA-Eu, and azide -DOTA-Sm tags. This approach allows direct quantification of the d-X in situ in the cell wall using 158 Gd, 153 Eu, and 154 Sm species-unspecific isotope dilution inductively coupled plasma mass spectrometry, avoiding any tedious and complex "cell-broken" pretreatment procedures that might induce racemization of the d-X. The obtained site-specific and accurate in situ information about the d-X enables quantitative monitoring of the bacterial response when Staphylococcus aureus meets vancomycin, showing that the amounts of azide -d-Leu and ketone -d-Met assembled are more important after determining the structure- and composition-dependent bacterial antibiotic resistance mechanisms. In addition, we found that the combined use of vancomycin and d-Ala restores the efficacy of vancomycin and might be a wise and simple way to combat vancomycin intermediate-resistant S. aureus .

In this study, we reported a facile, one-pot, and "green" synthesis of glutathione-protected gold nanoclusters (GSH@AuNCs) initiated by samarium (Sm 3+ ) lanthanides for the first time. Sm 3+ lanthanides more efficiently induced the formation of GSH@AuNCs with significantly enhanced luminescence than other lanthanides or heavy metal ions (Cd 2+ , Pb 2+ ) did. Using this strategy, a detection for Sm 3+ was made with a linearity range of (10.0-100.0 μM) and a limit of detection (LOD) of 0.5 μM. The Sm 3+ -based GSH@AuNCs were characterized by eco-friendliness, photostability, and low-cost synthesis with low biological toxicity and had great potential in the application for biosensing and bioimaging. They were successfully employed in the detection of dipicolinic acid (DPA), a well-reported biomarker for sensing potential infection by strongly hazardous anthrax spores. A good linear response was obtained for DPA detection ranging from 1.0 to 120.0 μM with a low LOD of 0.1 μM, which was much lower (600 times) than the infectious dosage of anthrax spores (6 × 10 -5 M). The detection was due to the strong binding affinity and strong chelation capability of DPA to Sm 3+ lanthanides, which caused the dissociation of the aggregates with an obvious decrease or even a turning-off effect of their luminescence.

Oxide based highly efficient narrow band red emitting phosphors are still a bottleneck in white LED applications. Trivalent europium ion based phosphors could be a better choice, however their weak oscillator strength restricts their use in white light emitting diodes (LEDs). Herein, we report a novel red emitting NaSrEu(MoO 4 ) 3 (NSEuM) phosphor with zero concentration quenching (non-layered crystal structure). The phosphors (NaSrY 1-x Eu x (MoO 4 ) 3 , x = 0.1-1, in increments of 0.1) were synthesized through a traditional solid-state reaction and their phase formations were analyzed by powder X-ray diffraction (PXRD) followed by Rietveld refinement. Under 395 nm excitation, all the phosphors showed sharp emission at 616 nm (full width at half maximum, FWHM ∼4-5 nm) owing to the 5 D 0 → 7 F 2 electric dipole transition of the Eu 3+ ion. A concentration dependent photoluminescence (PL) study revealed that there is no concentration quenching of the systems, leading to them having superior emission characteristics over those of commercial red phosphors as well as a reported Eu 3+ phosphor with a layered structure. The color purity of the synthesized phosphor was observed to be 96.32% and it shows excellent thermal stability at 423 K, retaining 64.6% of the emission intensity of its initial room temperature. The NSEuM phosphor shows a high absolute quantum yield of 79.7%. Besides this, a red LED (near UV (NUV) LED chip with the NaSrEu(MoO 4 ) 3 phosphor) as well as a hybrid white LED (NUV LED chip with an organic yellow dye + red NSEuM phosphor) were fabricated and their optical properties were studied. After the inclusion of the red phosphor in the hybrid white LED, the color rendering index (CRI)/correlated color temperature (CCT) were improved significantly (60/9333 K vs. 79/6004 K, respectively). In addition, to show the potential use of the system in plant growth application, we systematically investigated the Sm 3+ activation in NaSrY(MoO 4 ) 3 and found that the phosphor shows orange red emission with an intense deep red emission (645 nm ( 4 G 5/2 → 6 H 9/2 )). We fabricated a hybrid red/deep red LED by integrating a NUV LED with a mixed Sm 3+ and Eu 3+ phosphor and the spectral lines were well matched with the phytochrome (Pr) absorption spectrum. The presently investigated phosphor showed potential in a white LED as well as a deep red/orange-red LED for plant growth.

Ever since Hirata's report of yuzurimine in 1966, nearly fifty yuzurimine-type alkaloids have been isolated, which formed the largest subfamily of the Daphniphyllum alkaloids. Despite extensive synthetic studies towards this synthetically challenging and biologically intriguing family, no total synthesis of any yuzurimine-type alkaloids has been achieved to date. Here, the first enantioselective total synthesis of (+)-caldaphnidine J, a highly complex yuzurimine-type Daphniphyllum alkaloid, is described. Key transformations of this approach include a highly regioselective Pd-catalyzed hydroformylation, a samarium(II)-mediated pinacol coupling, and a one-pot Swern oxidation/ketene dithioacetal Prins reaction. Our approach paves the way for the synthesis of other yuzurimine-type alkaloids and related natural products.

Objectives: In this study, a new immunoassay for the simultaneous determination of pepsinogen I (PGI) and pepsinogen II (PGII) in serum based on element labeling strategy coupled with inductively coupled plasma mass spectrometry (ICP-MS) detection was proposed., Methods: The sandwich-type immunoassay was used to simultaneously detect PGI and PGII in serum. PGI and PGII were captured by anti-PGI and anti-PGII antibody immobilized on the magnetic beads and then banded with Eu 3+ labeled anti-PGI detection antibody and Sm 3+ labeled anti-PGII detection antibody, followed by ICP-MS detection., Results: The linear correlation coefficient (R 2 ) of PGI and PGII standard curves was .9938 and .9911, with the dynamic range of 0-200 ng/mL and 0-60 ng/mL, respectively. The limit of detection for PGI and PGII was 1.8 ng/mL and 0.3 ng/mL, respectively. The average recovery was 101.41% ± 6.74% for PGI and 101.47% ± 4.20% for PGII. Good correlations were obtained between the proposed method and CLIA (r = .9588 for PGI, r = .9853 for PGII)., Conclusions: We established a mass spectrometry-based immunoassay for the simultaneous detection of PGI and PGII in a single analysis. The element tagged immunoassay coupled with ICP-MS detection has high sensitivity, accuracy, and specificity in clinical serum sample analysis., (© 2020 The Authors. Journal of Clinical Laboratory Analysis published by Wiley Periodicals, Inc.)

This paper describes the synthesis of two beta-phosphorylamide ligands and their coordination chemistry with the Ln ions Tb 3+ , Eu 3+ , and Sm 3+ . Both the ligands and Ln complexes were characterized by IR, NMR, MS, and X-ray crystallography. The luminescence properties of the Tb 3+ and Eu 3+ complexes were also characterized, including the acquisition of lifetime decay curves. In the solid state, the Tb 3+ and Sm 3+ ligand complexes were found to have a 2:2 stoichiometry when analyzed by X-ray diffraction. In these structures, the Ln ion was bound by both oxygen atoms of each beta-phosphorylamide moiety of the ligands. The Tb 3+ and Eu 3+ complexes were modestly emissive as solutions in acetonitrile, with lifetime values that fell within typical ranges., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analysis, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Dosimetry properties of nanocrystalline SrSO 4 :Sm powders prepared via a co-participation method, were studied. X-ray diffraction, energy dispersive X-ray spectroscopy and Field emission scanning electron microscopy (FE-SEM) were used to investigate the structure, composition and morphology of nanocrystalline SrSO 4 :Sm powders. The nanocrystalline SrSO 4 :Sm powders had the orthorhombic crystal structure. FE-SEM image showed polygonal structure of particles with an average size of particles 0.2 μm. The thermoluminescence (TL) measurements for different concentration of samarium were done after gamma irradiation. TL glow curves showed the main glow peak at 370 °C. The maximum intensity of the TL glow curves for SrSO 4 :Sm was obtained with 0.05mol% concentration of Sm. Then, due to its high intensity glow curve, it was selected as the main sample. Furthermore, its dose-response, energy-response, and fading were studied in detail. Nanocrystalline SrSO 4 :Sm(0.05 mol%) powder had a linear dose-response approximately between 10Gy and 3 kGy. It showed energy dependence for low energy photons and its fading was less than 20% after 37 days. The X-ray excited luminescence (XEL), and TL were examined. The kinetic parameters were calculated by using the various TL analysis methods and OriginPro 8 software. The results showed the main TL glow peak obeyed second order kinetics., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This paper focuses on an optical study of a Tb 3+ /Bi 3+ -doped and Sm 3+ /La 3+ - doped Ca 2 Al 2 SiO 7 phosphor synthesized using combustion methods. Here, Ca 2 Al 2 SiO 7 :Sm 3+ showed a red emission band under visible light excitation but, when it co-doped with La 3+ ions, the emission intensity was further enhanced. Ca 2 Al 2 SiO 7 :Tb 3+ shows the characteristic green emission band under near-ultraviolet light excitation wavelengths, co-doping with Bi 3+ ions produced enhanced photoluminescence intensity with better colour tunable properties. The phosphor exhibited better phase purity and crystallinity, confirmed by X-ray diffraction. Binding energies of Ca(2p), Al(2p), Si(2p), O(1s) were studied using X-ray photoelectron spectroscopy. The reported phosphor may be a promising visible light excited red phosphor for light-emitting diodes and energy conversion devices., (© 2020 John Wiley & Sons, Ltd.)

Y 2 Zr 2 O 7 -doped with Eu 3+ and Sm 3+ phosphors were prepared for the first time as multifunctional smart materials using a solid-state reaction method at 1400 o C. Thermal behaviour, crystal structure, surface morphology, and elemental analysis were characterized using thermogravimetric (TG) and differential thermal (DTA) analyses, X-ray diffraction (XRD) and scanning electron microscope equipped with energy-dispersive X-ray spectroscopy (SEM-EDX). Experimental results revealed that both phosphors have a pyrochlore structure with a cubic crystal system. Photoluminescence properties were also measured and red emission was observed from Y 1.90 Eu 0.10 Zr 2 O 7 and Y 1.90 Sm 0.10 Zr 2 O 7 phosphors. Dielectric constant, loss tangent, piezoelectric charge constant, and Curie temperature of all the samples were determined using an LCR-meter, d 33 -meter, and TG/DTA. Eu doping in Y 2 Zr 2 O 7 resulted in a high dielectric constant (9.61) and low loss tangent (1.67%) values, whereas high piezoelectric charge constant (0.68 pC/N) and high Curie temperature (820°C) could be obtained using Sm-doped Y 2 Zr 2 O 7 ., (© 2020 John Wiley & Sons, Ltd.)

Recent studies have suggested that the anticancer activity of disulfiram (DSF, an FDA-approved alcohol-abuse drug) is Cu-dependent. Low system toxicity and explicit pharmacokinetic characteristics of DSF necessitate safe and effective Cu supplementation in local lesion for further applications. Herein, we presented a new conceptual 'nanosized coordination transport' strategy of Cu(ii) that was realized in porphyrin-based metal-organic frameworks, Sm-TCPP, with strong binding ability to Cu(ii) due to their coordination interactions. Sm-TCPP(Cu) was coated by hyaluronic acid (HA) that termed by Sm-TCPP(Cu)@HA, acting as 'beneficial horse' to target the tumor-localized HA receptor (CD44), thus liberating Cu(ii) ions in cellular overexpressed reductants. The CD44-mediated Cu(ii) accumulation efficiency of Sm-TCPP(Cu)@HA was benchmarked in vitro and vivo against the free TCPP (Cu) via ICP-MS analysis. More importantly, the sensitization effects of Sm-TCPP(Cu)@HA on the anticancer activity of DSF were demonstrated in vivo and in vitro. This study offered a new class of targeted Cu supplements to sensitize DSF for the effective treatment of cancer and established a versatile methodology for constructing a safe and specific delivery of metal ions within living organisms.

Microbeam radiation therapy (MRT) utilizes highly collimated synchrotron generated x-rays to create narrow planes of high dose radiation for the treatment of tumors. Individual microbeams have a typical width of 30-50 µm and are separated by a distance of 200-500 µm. The dose delivered at the center of the beam is lethal to cells in the microbeam path, on the order of hundreds of Grays (Gy). The tissue between each microbeam is spared and helps aid in the repair of adjacent damaged tissue. Radiation interactions within the peak of the microbeam, such as the photoelectric effect and incoherent (atomic Compton) scattering, cause some dose to be delivered to the valley areas adjacent to the microbeams. As the incident x-ray energy is modified, radiation interactions within a material change and affect the probability of interactions, as well as the directionality and energy of ionizing particles (electrons) that deposit energy in the valley regions surrounding the microbeam peaks. It is crucial that the valley dose between microbeams be minimal to maintain the effectiveness of MRT. Using a monochromatic x-ray source with x-ray energies ranging from 30 to 150 keV, a detailed investigation into the effect of incident x-ray energy on the dose profiles of microbeams was performed using samarium doped fluoroaluminate (FA) glass as the medium. All dosimetric measurements were carried out using a purpose-built fluorescence confocal microscope dosimetric technique that used Sm-doped FA glass plates as the irradiated medium. Dose profiles are measured over a very a wide range of x-ray energies at micrometer resolution and dose distribution in the microbeam are mapped. The measured microbeam profiles at different energies are compared with the MCNP6 radiation transport code, a general transport code which can calculate the energy deposition of electrons as they pass through a given material. The experimentally measured distributions can be used to validate the results for electron energy deposition in fluoroaluminate glass. Code validation is necessary for using transport codes in future treatment planning for MRT and other radiation therapies. It is shown that simulated and measured micro beam-profiles are in good agreement, and micrometer level changes can be observed using this high-resolution dosimetry technique. Full width at 10% of the maximum peak (FW@10%) was used to quantify the microbeam width. Experimental measurements on FA glasses and simulations on the dependence of the FW@10% at various energies are in good agreement. Simulations on energy deposited in water indicate that FW@10% reaches a local minimum around energies 140 keV. In addition, variable slit width experiments were carried out at an incident x-ray energy of 100 keV in order to determine the effect of the narrowing slit width on the delivered peak dose. The microbeam width affects the peak dose, which decreases with the width of the microbeam. Experiments suggest that a typical microbeam width for MRT is likely to be between 20-50 µm based on this work.

The oxidation process of samariumoxysulfide was studied in the temperature range of 500-1000 °C. Our DTA investigation allowed for establishing the main thermodynamic (∆Hº exp = -654.6 kJ/mol) and kinetic characteristics of the process (E a = 244 kJ/mol, A = 2 × 10 10 ). The enthalpy value of samarium oxysulfate (ΔHºf (Sm 2 O 2 SO 4(monocl) ) = -2294.0 kJ/mol) formation was calculated. The calculated process enthalpy value coincides with the value determined in the experiment. It was established that samarium oxysulfate crystallizes in the monoclinic symmetry class and its crystal structure belongs to space group C2/ c with unit cell parameters a = 13.7442 (2), b = 4.20178 (4) and c = 8.16711 (8)Å, β = 107.224 (1)°, V = 450.498 (9)Å 3 , Z = 4. The main elements of the crystalline structure are obtained and the cation coordination environment is analyzed in detail. Vibrational spectroscopy methods confirmed the structural model adequacy. The Sm 2 O 2 SO 4 luminescence spectra exhibit three main bands easily assignable to the transitions from 4 G 5/2 state to 6 H 5/2 , 6 H 7/2 , and 6 H 9/2 multiplets.

The structural, magnetic, electrical, and dilatation properties of the rare-earth NdCoO 3 and SmCoO 3 cobaltites were investigated. Their comparative analysis was carried out and the effect of multiplicity fluctuations on physical properties of the studied cobaltites was considered. Correlations between the spin state change of cobalt ions and the temperature dependence anomalies of the lattice parameters, magnetic susceptibility, volume thermal expansion coefficient, and electrical resistance have been revealed. A comparison of the results with well-studied GdCoO 3 allows one to single out both the general tendencies inherent in all rare-earth cobaltites taking into account the lanthanide contraction and peculiar properties of the samples containing Nd and Sm.

As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 μm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)