Unexpected Formation of 11(9→7)-abeo-Steroid Skeleton in Synthetic Studies toward Batrachotoxin.

Batrachotoxin (1) is a potent cardio- and neurotoxic steroid isolated from certain species of frogs, birds, and beetles. We previously disclosed two synthetic routes to 1. During our synthetic studies toward 1, we explored an alternative strategy for efficiently assembling its 6/6/6/5-membered steroidal skeleton (ABCD-ring). Here we report the application of intermolecular Weix and intramolecular pinacol coupling reactions. While Pd/Ni-promoted Weix coupling linked the AB-ring and D-ring fragments, SmI2-mediated pinacol coupling did not cyclize the C-ring. Instead, we discovered that SmI2 promoted a 1,4-addition of the α-alkoxy radical intermediate to produce the unusual 11(9→7)-abeo-steroid skeleton. Thus, this study demonstrates the convergent assembly of the skeleton of the natural product matsutakone in 11 steps from 2-allyl-3-hydroxycyclopent-2-en-1-one.

Luminescence of Sm3+ in double perovskite-type Ba2SrWO6 for insect trapping.

The predominant method for pest control has been the use of pesticides, which have been shown to have detrimental effects on soil, freshwater, and crop quality. Therefore, the development of novel and sustainable crop protection strategies has become increasingly imperative. In this study, a novel orange-red emitting Ba2SrWO6: Sm3+ phosphor was synthesized using the high-temperature solid-state reaction. Under ultraviolet excitation, the phosphors showed obvious emission peaks at 575, 614, and 662 nm. The Ba2SrWO6: Sm3+ was used to fabricate a fluorescence film with polydimethylsiloxane (PDMS), and attracted twice as many insects as the blank control group under 365 nm ultraviolet light. This material holds great potential as a fluorescent agent for insect trapping in the pest control fields of tea, cotton, eggplant, rice, potato, grape, and other agricultural industries. Our findings provide an eco-friendly approach to pest management for the increment of food production.

Structural, photoluminescence, and optical characteristics of a Sm3+ -doped lead borate-strontium-tungsten glass system: Evaluation of Judd-Ofelt intensity parameters and radiative properties.

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 Sm3+ ions were investigated via Fourier transform infrared (FTIR) spectroscopy. FTIR analysis revealed B-O-B bridges, BO3 , and BO4 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 G5/2 to the excited states 6 H5/2 , 6 H7/2 , 6 H9/2 and 6 H11/2 and J-O theory was utilized to study these optical transitions for Sm3+ ions. Calculations of the oscillator strengths and J-O intensity parameters were performed and the obtained J-O parameters followed the sequence Ω4 > Ω6 > Ω2 . 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.

Development of samarium-doped phosphate glass microspheres for internal radiotheranostic applications.

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, 90Y, is currently used for internal radiotherapy. However, theranostic radionuclide-doped microspheres can be developed by incorporating 153Sm, 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. 60P2O5-25CaO-15Na2O) was mixed with Sm2O3 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 × 1013 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.

The association between levels of samarium, hafnium, tungsten and rhenium in seminal plasma and the risk of idiopathic oligo-astheno-teratozoospermia in men of childbearing age.

Oligo-astheno-teratozoospermia (OAT) is a global public health problem, which affects 30% men of childbearing age. Meanwhile, with the rapid development of industry and economy, the contents of rare earth elements (REEs) in the environment are increasing. However, little is known about the associations between REEs levels and OAT risk. To evaluate the associations between the levels of four REEs (samarium (Sm), hafnium (Hf), tungsten (W), rhenium (Re)) in seminal plasma and OAT risk, from October 2021 to November 2022, semen samples from 924 men of childbearing age (460 controls and 464 cases) were collected from the reproductive center of the First Affiliated Hospital of Anhui Medical University. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to measure the levels of Sm, Hf, Re and W in seminal plasma. Bayesian kernel machine regression (BKMR) was conducted to explore the joint effects of levels of four REEs in seminal plasma on the risk of OAT and select the one exerting a major role; generalized linear regression models (GLM) with log link function were employed to investigate the association of every REE level in seminal plasma and OAT risk; sankey diagram and linear regression models were utilized to describe the associations between the levels of four REEs and the indexes of sperm quality. The levels of four REEs in seminal plasma were higher in the case group than levels in the control group (pSm = 0.011, pHf = 0.040, pW = 0.062, pRe = 0.001, respectively). In BKMR analysis, the OAT risk increased when the overall levels of four REEs were higher than their 55th percentile compared to all of them at their 50th percentile, and Re level played a major role in the association. Additionally, Re level in seminal plasma was positively associated with  the OAT risk in the single element model after adjustment of covariates (medium vs. low: OR (95% CI) = 1.55 (1.10, 2.18); high vs. low: OR (95% CI) = 1.69 (1.18, 2.42)). Lastly, the sankey diagram and linear regression models revealed that Sm level was negatively associated with the PR%, total sperm count and total progressively motile sperm count; Hf level was negatively associated with the PR%; W and Re levels were negatively associated with the PR% and total motility, and Re level was positively associated with abnormal morphology rate. Men of childbearing age with OAT had higher levels of Sm, Hf and Re in seminal plasma than those in the control group. An increasing trend for the OAT risk was observed with an increase in mixture levels of Sm, Hf, W and Re, and Re exposure level played a major role in the association whether in BKMR model or single element model. Additionally, the levels of these four REEs were negatively associated with the indexes of sperm quality.

Novel Ag-modified vanadate nanosheets for determination of small organic molecules with laser desorption ionization mass spectrometry.

Laser desorption ionization mass spectrometry (LDI-MS) aroused intensive concerns for the merits of label-free and high-throughput analysis. Here, we designed a silver nanoparticles (AgNP)-modified indium vanadate nanosheets with doping samarium (AgNP@InVO4:Sm) nanosheets. The developed AgNP@InVO4:Sm nanosheets (AIVON) were synthesized based on the microemulsion-mediated solvothermal method and ultraviolet-assisted in situ formation of AgNP, then for the first time applied as a matrix in LDI-MS analysis. With the advantages including enhanced MS signal, little matrix-related background, high reproducibility, and good salt tolerance, AIVON exhibited much better prospect than non-modified indium vanadate nanosheets with doping samarium (IVON) and traditional organic matrix, thus allowing sensitive MS detection for a wide range of low-molecular-weight (LMW) molecules. Moreover, by coupling with headspace sampling thin-film microextraction (TFME), a kind of representative pollutant chlorophenols were identified and quantified via AIVON-assisted LDI-MS in environmental and biological samples. Volatile LMW pollutants could be preconcentrated after TFME, hence a sensitive and rapid assay with negligible sample matrix effect was realized by using AIVON-assisted LDI-MS. It is anticipated that this novel nano-matrix AIVON and the proposed TFME coupling detection strategy were of competitive merits for LDI-MS analysis in the fields of environment, biomedicine, and agriculture.

Effects of rare earth element samarium doped zinc oxide nanoparticles on Mytilus galloprovincialis (Lamarck, 1819): Filtration rates and histopathology.

BACKGROUND: Doping was reported to improve the photo catalytic performance, antioxidant, antibacterial and other biological properties of nanoparticles. While, improving the nanoparticle properties, doping could change toxicity profile to living organism. Hence, the aim of this work was to assess the effects of samarium doped zinc oxide nanoparticles (Sm doped ZnO NPs) on the edible mussel Mytilus galloprovincialis. METHODS: Sm doped ZnO nanoparticles were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) techniques. 156 mussels were exposed during 7 days to a low, intermediate and high concentration of Sm doped ZnO NPs (0.5, 1 and 1.5 mg/L, respectively). The filtration rates were assessed after 1 and 2 h. Histopathological alterations were determined in gills, digestive glands and gonads using a quantitative analysis. RESULTS: The filtration rates decreased in all individuals exposed to Sm doped ZnO NPs, a significant decrease was noted with the low and intermediate concentration (0.5 and 1 mg/L) of Sm doped ZnO NPs after 1 and 2 h, respectively. The histopathological index (Ih) estimated for gills, digestive glands and gonads showed differences depending on the organ and the nanoparticle concentration. The highest Ih were reported for digestive glands and female gonads exposed to the intermediate concentration (1 mg/L) of Sm doped ZnO NPs. As for gills and male gonads, the highest Ih were noted with the high concentration (1.5 mg/L) of Sm doped ZnO NPs. CONCLUSION: Results from this study revealed the toxicity of Sm doped ZnO NPs in Mytilus galloprovincialis gills, digestive glands and gonads. The toxicity induced by this nanoparticle varies depending on the organ and the concentration.

Adjustable luminescence copper nanoclusters nanoswitch based on competitive coordination of samarium ions for cascade detection of adenosine triphosphate and acid phosphatase activity.

Benefit from the strong coordination property, lanthanide metal ions have been used as competitive reagents to modulate the fluorescence changes of the system. However, lanthanide metal ions as inducers for aggregation-induced emission enhancement in nanosystems is rare. Herein, we report a "turn on-off-on" fluorescent switch for cascade detection of acid phosphatase (ACP) and adenosine triphosphate (ATP) based on the competitive coordination of samarium ions (Sm3+). Novel copper nanoclusters (CuNCs) with long wavelength emission (614 nm) stabilized by glutathione (GSH) and glycylglycine (Gly-Gly) have been confirmed to have AIE property. With the continuous aggregation of GSH/Gly-Gly CuNCs under the induction of Sm3+, the fluorescence of the system increased to achieve the "turn-on" process. The coordinated behaviour between Sm3+ and GSH/Gly-Gly CuNCs is discussed. Due to the strong metal coordination ability of ATP, the Sm3+ coordinated with the GSH/Gly-Gly CuNCs is competed out, resulting in the fluorescence "turn-off" process of the system. As the substrate of enzymatic hydrolysis of ACP, with the continuous hydrolysis of ATP by ACP, Sm3+ coordinates with GSH/Gly-Gly CuNCs again, which leads to the AIE effect and realize the fluorescence "turn-on" process of the system. This strategy results in ATP linear range of 0.508 ~ 120.0 µM with a detection limit of 0.508 µM (S/N = 3) and ACP linear range of 0.011 ~ 30.0 U·L-1 with a detection limit of 0.011 U·L-1 (S/N = 3). Application to biologic samples was successful.

Visible light-active samarium manganite nanostructures for enhanced water-soluble pollutant degradation.

In this study, a green approach was used to synthesize SmMnO3 magnetic nanoparticles via the auto combustion method, where pomegranate juice was utilized as a natural fuel. The concentration of fuel was varied to investigate its effect on the purity and morphology of SmMnO3 nanoparticles. The physiochemical properties of the synthesized nanoparticles, including crystal structures, morphology, optical, and magnetic properties, were investigated using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier-Transform Infrared Spectroscopy (FTIR), Vibrating Sample Magnetometer (VSM), Diffuse Reflectance Spectroscopy (DRS), X-ray fluorescence (XRF) and Brunauer-Emmett-Teller (BET). The band gap of the as-synthesized nanoparticles was determined to be 1.8 eV, indicating their potential as a photocatalyst. The photocatalytic activity of SmMnO3 nanoparticles was evaluated against Methyl violet and Erythrosine, and the mechanism of photocatalyst was determined using EDTA, benzoic acid, and benzoquinone as scavengers. Photocatalytic activity was studied in both UV and visible light, and it was found that the maximum degradation (94%) was related to the degradation of Erythrosine (10 ppm) in the presence of visible light. The stability test of SmMnO3 performed and confirmed the stability of nanoparticles after 5 cycles. The results suggest that SmMnO3 nanoparticles synthesized via the green auto combustion method using pomegranate juice as a natural fuel can serve as a promising photocatalyst for the degradation of organic pollutants in the environment. Further studies can be conducted to investigate their potential in other applications.

Efficient Photocatalytic degradation of direct blue 15 dye using samarium doped bismuth tungstate nanosheets: A sustainable approach towards wastewater treatment.

The rare earth metal, samarium (Sm3+) doped bismuth tungstate (Bi2WO6) nanoparticles were prepared by a one-pot hydrothermal method. The powder X-ray diffraction (XRD) analysis confirmed the formation of Bi2WO6 with an orthorhombic crystal structure. The crystallite size of Bi2WO6 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 Sm3+ doped Bi2WO6 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 Sm3+ doped bismuth tungstate. The energy dispersive X-ray (EDX) spectrum of Sm3+ doped Bi2WO6 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 Sm3+ doped Bi2WO6 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 Sm3+ concentration. The obtained results demonstrated that the Sm-Bi2WO6 nanosheets could provide an effective and sustainable solution for treating the wastewater containing direct blue 15 dye.

One-step electrodeposition preparation of boron nitride and samarium co-modified Ti/PbO2 anode with ultra-long lifetime: highly efficient degradation of lincomycin wastewater.

Lincomycin (LC) is an extensively applied broad-spectrum antibiotic, and its considerable residues in wastewater have caused a series of environmental problems, which makes degradation of LC wastewater extremely urgent. In this work, we have constructed a novel boron nitride (BN) and samarium (Sm) co-modified Ti/PbO2 as anode for high-performance degradation of LC wastewater. Compared with Ti/PbO2, Ti/PbO2-Sm, and Ti/PbO2-BN electrodes, Ti/PbO2-BN-Sm electrode with smaller pyramidal particles possesses higher oxygen evolution potential (2.32 V), excellent accelerated service life (103 h), and outstanding electrocatalytic activity. The single-factor experiments demonstrate that under optimized conditions (current density of 20 mA.cm-2, 6.0 g L-1 Na2SO4, pH 9, and temperature of 30°C), removal rate and COD degradation rate of LC at 3 h have reached 92.85% and 89.11%, respectively. At the same time, degradation of LC is in accordance with the primary kinetic model. Based on the analysis of high-performance liquid chromatography-mass spectrometry (HPLC-MS), four possible degradation pathways are hypothesized. Therefore, efficient electrochemical degradation of LC by using an extremely long-life Ti/PbO2 electrode with high catalytic activity may be a promising method.

Multicomponent Assembly of Bicyclic Aza-peroxides Catalyzed by Samarium Complexes and Their Cytotoxic Activity.

An original strategy toward bridged tetraoxazaspirobicycloalkanes was developed. The synthesis is based on a three-component condensation-cyclization reaction of primary arylamines with 1,1'-peroxybis (1-hydroperoxycycloalkanes) and pentane-1,5-dial catalyzed by Sm(NO3)3·6H2O. The structures and conformations of the products were determined by X-ray diffraction analysis and 1H and 13C NMR spectroscopy. High cytotoxic activity and biological potential toward ferroptosis induction were found for the synthesized bicyclic aza-peroxides.

Regioselective SmI2-Mediated Radical ipso-Substitution Cyclization for the Construction of Pyrrolophenanthridinone Skeletons: The Synthesis of Amaryllidaceae Alkaloids.

Here, we report a regioselective, samarium(II) diiodide mediated intramolecular radical ipso-substitution cyclization. Through the use of a methoxy group as a leaving group, it was possible to regulate the regioselectivity of the reaction by changing the temperature and additives. We applied the developed reaction to the synthesis of four Amaryllidaceae alkaloids and have shown that the present reaction successfully overcomes regioselectivity issues encountered with other cyclization methods.

Orange-red luminescence of samarium-doped bismuth-germanium-borate glass for light-emitting devices.

Samarium (Sm3+ )-doped glass has sparked a rising interest in demonstrating a noticeable emission in the range of 400-700, which is advantageous in solid-state lasers in the visible region, colour displays, undersea communication, and optical memory devices. This study reports the fabrication of Sm3+ -doped bismuth-germanium-borate glasses were established using a standard melt-quenching technique and inspection by absorption, steady-state luminescence, and transient studies. The typical peaks of Sm3+ ions were detected in the visible range under 403 nm excitation. A strong emission band was detected at 599 nm that resembles the 4 G5/2 →6 H7/2 transition of Sm3+ ions for BGBiNYSm0.5 glass. Furthermore, a reddish-orange (coral) luminescence at 646 nm that resembles the 4 G5/2 →6 H9/2 transition was also perceived. The stimulated emission cross-section of 4 G5/2 level for BGBiNYSm0.5 glass was 0.39 × 10-22  cm2 . Lifetime of the 4 G5/2 level was enhanced for the BGBiNYSm0.5 glass and decreased with an increase in active ion concentrations. The lifetime quenching of ions at the metastable state was because of energy transfer among Sm3+ ions by cross-relaxation channels. Commission Internationale de l'Éclairage (CIE) coordinates were evaluated from the emission spectra. Moreover, all the findings recommend these glass as light-emitting materials in the coral region at 599 nm for solid-state lighting applications.

Phase I evaluation of CycloSam® (Sm-153-DOTMP) bone seeking radiopharmaceutical in dogs with spontaneous appendicular osteosarcoma.

153 Sm-DOTMP (CycloSam® ) is a newly-patented radiopharmaceutical for bone tumor treatment. DOTMP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethylene-phosphonate) is a macrocyclic chelating agent with superior binding properties to 153 Sm when compared with EDTMP (Quadramet™, used for palliative treatment of bone cancer). CycloSam® was administered at 1 mCi/kg (37 MBq/kg) in a prospective pilot study to seven dogs with bone cancer resulting in no myelosuppression. Then, 13 dogs were enrolled in a prospective clinical trial study using traditional 3+3 dose escalation and starting at 1.5 mCi/kg. Baseline evaluation included hematologic and biochemical testing, diagnosis confirmation, thoracic and limb radiographs, technetium-99 m-HDP bone scintigraphy, and 18 F-FDG PET scan (SUVmax). Toxicity (primary endpoint) was assessed through weekly blood counts and adverse events. Dogs received 1.5 mCi/kg (n = 4), 1.75 mCi/kg (n = 6), and 2 mCi/kg (n = 3) of 153 Sm-DOTMP. Dose-limiting neutropenia and thrombocytopenia were seen at 2 mCi/kg. No dose-limiting nonhematologic toxicities occurred. Efficacy (secondary endpoint) was assessed by objective lameness measurement (body-mounted inertial sensors), owner quality-of-life (QoL) questionnaire, and repeat PET scan. Objective lameness measurement improved in four dogs (53%-60% decrease) was equivocal in three dogs, and worsened in four dogs (66%-115% increase); two dogs were not evaluable. Repeat 18 F-FDG PET scan results varied and change in lameness did not consistently correlate with SUVmax changes. QoL score worsened (n = 5) or was improved/stable (n = 7). Carboplatin chemotherapy (300 mg/m2 IV every 3 weeks ×4) started 4 weeks after 153 Sm-DOTMP injection. No dog died of chemotherapy-related complications. All dogs completed study monitoring. The recommended dose for CycloSam® in dogs is 1.75 mCi/kg, which resulted in some pain control with minimal toxicity and was safely combined with chemotherapy.

Phase-change Fano resonator for active modulation of thermal emission.

Optical modulation of heat emission using spectrally selective infrared (IR) metasurface nanoantenna designs has found potential applications in various fields, including radiative cooling and thermal camouflage. While radiative cooling requires emitters to emit within atmospheric transmissive windows (mainly located at 8-14 µm), thermal camouflage structures have to operate within the non-transmissive window (5-8 µm) to hide an object from thermal imaging systems and cameras. Therefore, a passive nanoantenna structure cannot satisfy both conditions simultaneously. In this paper, we propose an adaptive nanoantenna emitter made of samarium nickelate (SmNiO3) phase change material to cover both functionalities with a single Fano resonator-based design. As the temperature rises, the thermal signature of the nanoantenna at the transmissive window is suppressed; therefore, a better camouflage performance is achieved. The dynamic tunability of switching from radiative cooling to thermal camouflage of the proposed Fano resonator-based design is quantitatively demonstrated using emissive power calculations under different conditions.

Designing nano ranged electrode modifier comprised of samarium niobate anchored carbon nanofibers for trace level detection of food colourant: Tartrazine.

Tartrazine (TRZ) is a predominantly used food color in food processing industries which is soluble in water to produce a orange colour. This food colorant is categorized under the mono-azo pyrazolone dye group known for the perilous azo group (-NN-) attached to the aromatic ring that threatens human health. In consideration of these aspects, a novel TRZ sensing platform with advanced electrode material is designed by incorporating nanotechnology with chemical engineering. This innovative sensor is prepared by electrode modification through a nano ranged electrode modifier of SmNbO4 decorated on the enmeshed carbon nanofibers. This is the first report on the investigation of SmNbO4/f-CNF as an electrode modifier to extricate the superlative electrochemical properties towards TRZ detection and protracted its practicality to food samples with a lower limit of detection (2 nmolL-1), broad linear range, good selectivity, and functional stability.

Cerium and samarium blocked antioxidant enzymes in wheat plants.

This work was conducted to study positive and negative impacts of cerium (Ce) and samarium (Sm) on two cultivars (Arta and Baharan) in wheat plant. Symbols of stress such as proline, malondialdehyde (MDA) and antioxidant enzymes, which may be complicated in the suppression responses of plants, were also studied. Wheat plants were exposed to 0, 2500, 5000, 7500, 10,000 and 15,000 µM of Ce and Sm for 7 days. The growth enhanced in plants treated with lesser Ce and Sm concentration (2500 µM) and declined in plants treated with upper concentrations as compared to untreated plants. The treatment with 2500 µM of Ce and Sm increased dry weigh in Arta by 68.42 and 20% and in Baharan by 32.14% and 27.3%. Thus, Ce and Sm had hormesis effect on growth in wheat plants. According to plant's growth parameter patterns, Arta cultivar had more sensitive to Sm than to Ce, whereas Baharan cultivar had sensitive to Ce than to Sm. Our results indicated impact of Ce and Sm on proline accumulation depended on the dosage of Ce and Sm. It was observed that Ce and Sm accumulated in wheat plants at higher exposure doses. Increment of MDA content by Ce and Sm treatments showed that these metals caused oxidative stress in wheat plants. Ce and Sm blocked enzymatic antioxidant system (superoxide dismutases, peroxidase and polyphenol peroxidase) in wheat. In wheat plants treated with lower Ce and Sm concentrations higher amounts of non-enzymatic antioxidant metabolites were detected. Thus, we showed the potential negative impact of unsuitable utilization of REEs in plants and suggested growth and interruption in physiological and biochemical mechanisms as a possible factor to recognize the underlying toxicological processes.

Highly selective and discriminative detection of small alcohols based on a dual-emission macrocyclic samarium complex.

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 (H2L2r) 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, C5H9OH and C6H11OH, 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.

Acute toxicity of single and combined rare earth element exposures towards Daphnia similis.

The increasing use of Rare Earth Elements (REE) in emerging technologies, medicine and agriculture has led to chronic aquatic compartment contamination. In this context, this aimed to evaluate the acute toxic effects of lanthanum (La), neodymium (Nd) and samarium (Sm), as both single and binary and ternary mixtures on the survival of the microcrustacean Daphnia similis. A metal solution medium with (MS) and without EDTA and cyanocobalamin (MSq) as chelators was employed as the assay dilution water to assess REE bioavailability effects. In the single exposure experiments, toxicity in the MS medium decreased following the order La > Sm > Nd, while the opposite was noted for the MSq medium, which was also more toxic than the MS medium. The highest MS toxicity was observed for the binary Nd + La (1:1) mixture (EC50 48 h of 11.57 ± 1.22 mg.L-1) and the lowest, in the ternary Sm + La + Nd (2:2:1) mixture (EC50 48 h 41.48 ± 1.40 mg.L-1). The highest toxicity in the MSq medium was observed in the single assays and in the binary Sm + Nd (1:1) mixture (EC50 48 h 10.60 ± 1.57 mg.L-1), and the lowest, in the ternary Sm + La + Nd (1:2:2) mixture (EC50 48 h 36.76 ± 1.54 mg.L-1). Concerning the MS medium, 75 % of interactions were additive, 19 % antagonistic, and 6 % synergistic. In the MSq medium, 56 % of interactions were synergistic and 44 % additive. The higher toxicity observed in the MSq medium indicates that the absence of chelators can increase the concentrations of more toxic free ions, suggesting that the MS medium should be avoided in REE assays. Additive interactions were observed in greater or equivalent amounts in both media and were independent of elemental mixture ratios. These findings improve the understanding of environmental REE effects, contributing to the establishment of future guidelines and ecological risk calculations.