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BACKGROUND: Prior to soil formation, phosphate liberated by rock weathering is often sequestered into highly insoluble lanthanide phosphate minerals. Dissolution of these minerals releases phosphate and lanthanides to the biosphere. Currently, the microorganisms involved in phosphate mineral dissolution and the role of lanthanides in microbial metabolism are poorly understood. RESULTS: Although there have been many studies of soil microbiology, very little research has investigated microbiomes of weathered rock. Here, we sampled weathered granite and associated soil to identify the zones of lanthanide phosphate mineral solubilisation and genomically define the organisms implicated in lanthanide utilisation. We reconstructed 136 genomes from 11 bacterial phyla and found that gene clusters implicated in lanthanide-based metabolism of methanol (primarily xoxF3 and xoxF5) are surprisingly common in microbial communities in moderately weathered granite. Notably, xoxF3 systems were found in Verrucomicrobia for the first time, and in Acidobacteria, Gemmatimonadetes and Alphaproteobacteria. The xoxF-containing gene clusters are shared by diverse Acidobacteria and Gemmatimonadetes, and include conserved hypothetical proteins and transporters not associated with the few well studied xoxF systems. Given that siderophore-like molecules that strongly bind lanthanides may be required to solubilise lanthanide phosphates, it is notable that candidate metallophore biosynthesis systems were most prevalent in bacteria in moderately weathered rock, especially in Acidobacteria with lanthanide-based systems. CONCLUSIONS: Phosphate mineral dissolution, putative metallophore production and lanthanide utilisation by enzymes involved in methanol oxidation linked to carbonic acid production co-occur in the zone of moderate granite weathering. In combination, these microbial processes likely accelerate the conversion of granitic rock to soil.

The introduction of the cerium(III) analogue (1‐Ce, Ln = Ce) of (tert‐butoxido)chloridopentakis(tetrahydrofuran)lanthanide(III) tetraphenylborate tetrahydrofuran disolvate, [Ln{OC(CH3)3}Cl(C4H8O)5][B(C6H5)4]·2C4H8O or [Ln(OtBu)Cl(THF)5](BPh4)·2THF (1‐Ln) has been achieved with a structural comparison between the existing solid‐state structures of other rare earth analogues and the title compound at 100 and 180 K. The cation in 1‐Ce is targeted as the cerium(III) ion possesses the criteria to exhibit slow magnetic relaxation in axial point‐charge crystal fields, akin to the dysprosium(III) ion in 1‐Dy. AC magnetic susceptibility experiments reveal no such behaviour for 1‐Ce, putting the viability of cerium‐based SMMs into question. [ABSTRACT FROM AUTHOR]

New copolymers of vinylphosphonic and p‐methacrylamidobenzoic acids of varying compositions were synthesized via free radical copolymerization. The structure of the obtained polymers was confirmed by NMR and FTIR spectroscopy. As the proportion of vinylphosphonic acid in the initial reaction mixture increased, the yield of the copolymer and its molecular mass both decreased. The synthesized copolymers were found to form stable soluble luminescent complexes in dilute aqueous solutions, with a concentration range of 0.002 to 0.02 mg/ml. An increase in the concentration of vinylphosphonic acid moieties in copolymers was accompanied by a noticeable decrease in the luminescence intensity. The new copolymers' ability to bind efficiently with lanthanide ions renders them a promising material for the design of polymeric contrast agents, preparations for radioimmunotherapy and photodynamic therapy. [ABSTRACT FROM AUTHOR]

In this semi‐quantitative study, laser crystal microparticles which are potentially capable of generating mid‐infrared (MIR) light are incorporated into MIR transmitting optical fibers using a volumetric interface doping technique that combines interface doping with volumetric doping. Using confocal microscopy with a refractive index matching fluid, the Er:YAP microcrystals (MCs) inside the tellurite glass fiber are observed based on the detection of the green upconversion fluorescence emission of Er3+ ions, produced under excitation at 976 nm and localized at the central region within the fiber. The key outcome from this proof‐of‐concept study is that MC particles that are fused with the glass during the fiber drawing process survived heat treatment because the MC particles are exposed for a short time to a glass fluid with high viscosity of ≈105 Pa.s, which prevented the glass from exerting a dissolution effect. The survival of the MCs demonstrated the viability of the doping technique for fabricating fibers with exotic crystal‐glass combinations for applications including good refractive index matching across the pump and lasing bands of rare earth ions. This latter parameter provides significant particle size flexibility whilst minimizing additional loss from scattering especially at MIR wavelengths where the MC diameter‐to‐wavelength ratio becomes smaller. [ABSTRACT FROM AUTHOR]

The imidophosphorane ligand, [NPtBu3]− (tBu=tert‐butyl), enables isolation of a pseudo‐tetrahedral, tetravalent praseodymium complex, [Pr4+(NPtBu3)4] (1‐Pr), which is characterized by a suite of physical characterization methods including single‐crystal X‐ray diffraction, electron paramagnetic resonance, and L3‐edge X‐ray near‐edge spectroscopies. Variable‐temperature direct‐current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce3+ analogue, driven by increased crystal field. The four‐coordinate environment around Pr4+ in 1‐Pr, which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin‐orbit coupling in a molecular tetravalent lanthanide within a pseudo‐tetrahedral coordination geometry. [ABSTRACT FROM AUTHOR]

The dinitrogen (N2) chemistry of lanthanides remains less developed compared to the d‐block metals and lanthanide‐promoted N2 functionalization chemistry in well‐defined lanthanide complexes remains elusive. Here we report the synthesis and characterization (SQUID, EPR, DFT, X‐Ray) of the siloxide supported heterobimetallic (Tm/K) complexes [{KTm(OSi(OtBu)3)3}2(μ‐η2 : η2‐N2)] (1) and [K3{Tm(OSi(OtBu)3)3}2(μ‐η2 : η2‐N2)] (2). Complex 2 provides a rare example of a metal complex of the triply reduced N23− radical. The structure of 2 differs from the few previously reported N23− complexes as it presents two Tm and three K cations binding the N23− radical, facilitating N2 functionalization. Notably, the K3Tm2‐bound N23− moiety reacts with excess H+ to form NH4Cl in 18 % yield, and with MeOTf at room temperature to yield the dimethyl hydrazido complex [K2{Tm(OSi(OtBu)3)3}2(μ‐(CH3)NN(CH3))] (3). Protonolysis of 3 yields MeHN−NMeH ⋅ 2HCl in 18 % yield. [ABSTRACT FROM AUTHOR]

Here we report on the Magneto‐Chiral Dichroism (MChD) detected through visible and near‐infrared light absorption of two enantiomeric pairs of ErIII and TmIII chiral complexes featuring a propeller‐like molecular structure. The magnetic properties show typical features of isolated paramagnetic ions associated with 4I15/2 and 3H6 ground state terms. MChD spectroscopy shows high gMChD dissymmetry factors of ca. 0.12 T−1 and 0.05 T−1 (T=4.0 K and B=1.0 T) for ErIII and TmIII, respectively, associated with the magnetic‐dipole allowed 4I13/2 ← 4I15/2 and 3H5 ← 3H6 transitions. MChD signals of the two complexes were detected up to room temperature and under magnetic fields up to 5.0 T. For the first time, the MChD results are discussed in the context of the Richardson theory of lanthanide optical activity and provide clear indications on the strongest MChD‐active electronic transitions of lanthanide complexes. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Two families of cyclopentadienyl (Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes, namely [Ln{η5:σ‐Me2C(C5H4)(C2B10H10)}2][Li(DME)3] (1Ln, Ln = Tb, Dy, Ho, Er) and [2‐THF‐2'‐(μ2‐Cl)Li(THF)3‐2,2'‐Ln(nido‐1,7‐C2B9H11)Cp*] (2Dy), were synthesized. Family of 1Ln has been proposed based on the mixing‐ligands idea by linking Cp and nido‐dicarborllide. However, the carborane cage of [Me2C(C5H4)(C2B10H10)]2− deprotons and forms a mono‐C− anion rather than deboron to form dicarborllide dianion. Hence, the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C− anions of carborllides. Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings. In this cubic‐type geometry, no significant magnetic axiality is presented; only 1Dy and 1Tb show field‐induced slow magnetic relaxation behavior below 10 K. Inspired by 1Ln, the free pentamethylcyclopentadienyl (Cp*−) and nido‐dicarborllide ligands are used to sandwich central Dy3+ ion, achieving heteroleptic complex 2Dy. The bending angle by linking the centroid of Cp*−, Dy3+ and C2B32− in 2Dy is increased to 132.8(1)°. As such, the effective energy barrier for magnetic reversal (Ueff) and magnetic blocking temperature TB (ZFC) are both increased (Ueff = 616(10) K; TB = 6 K). The effort of further enhancing Ueff and TB in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality. [ABSTRACT FROM AUTHOR]

A detailed mechanistic probe of the organolanthanide‐mediated tandem insertion/annulation of alkynylbenzonitriles with secondary amines by an archetypical homoleptic lanthanum silylamide starting material is presented. An in‐depth computational scrutiny of alternatively plausible pathways for relevant productive steps and also performance‐degrading pathways identified the pathway likely traversed in productive catalysis. It entails the transformation of the starting material into various of silylamide/amide compounds, of which the lanthanum bis‐silylamide/amide is thermodynamically prevalent, capable of promoting the process. Benzonitrile insertion is irreversible to readily afford the lanthanum amidinate, which can adopt various easily interconvertible ligation pattern. The rather rapid protonolysis of the La─N imine linkage would lead to undesirable aminoamidines, but its net endergonicity renders this performance‐degrading avenue nonviable. Instead, the lanthanum amidinate is converted back into catalytically competent lanthanum bis‐silylamide/amide with the release of the observed aminoisoindole product. This transformation favors a stepwise insertative cyclisation/La─C alkenyl protonolysis sequence over an otherwise kinetically noncompetitive proton‐triggered stepwise N─C/C─H bond forming process. The operative insertative pathway comprises turnover‐limiting and irreversible insertion of the alkyne C≡C tether into the La─N amidinate linkage followed by La─C alkenyl aminolysis at the intervening lanthanum alkenylisoindinyl intermediate. The DFT‐assessed barrier for turnover‐limiting insertative N─C ring closure favorably compares with reported performance data. [ABSTRACT FROM AUTHOR]

Magnetic circularly polarized luminescence (MCPL) is a technique based on the differential emission of left and right circularly polarized light induced by a magnetic field. This technique is the emission counterpart of to the widely explored magnetic circular dichroism. In this work, the first demonstration of MCPL is presented in heterometallic lanthanide(III) systems by using two molecular cluster aggregates, {Eu1Tb19} and {Eu3Tb17}. The results presented here indicate the potential that MCPL holds for obtaining highly tuned magneto‐optical materials for various applications, such as anti‐counterfeiting materials. Additionally, the findings suggest that magnetic interactions between the ions modulate the dissymmetry factor, opening the possibility of the development of highly tunable MCPL materials. [ABSTRACT FROM AUTHOR]

The potential impact of the parity non‐conserving (PNC) weak nuclear interaction on the chirality of a nascent chiral carbon center has previously been examined in the context of evolutionary models for enantiomeric selectivity in the formation of natural amino acids and nucleic acids. Since the PNC effect is the only inherently handed property in nature, it is an obvious candidate to consider in those cases where there is a natural selectivity for a specific enantiomer, including the molecular building blocks of the molecules of life. Over geological timeframes, the potential impact of the PNC weak nuclear force on chiral preference appears feasible. Key requirements included an autocatalytic reaction cycle and involvement of metal‐ion catalysts. While prior studies offer no feasible path to experimentally test the hypothesis; the Z5‐dependence of the PNC interaction does suggest that catalysis by heavy elements could yield observable chiral preferences within an experimentally accessible timeframe. Calculations of the magnitude of the effect are presented for select heavy‐elements and it is shown that chiral preference could be observed within a time span of weeks to months when such metals are used to promote amino acid synthesis via an autocatalytic Strecker reaction. [ABSTRACT FROM AUTHOR]

We report the preparation, isolation, and reactivity of gas‐phase lanthanide nitrate and acetate complexes featuring the elusive trivalent LnIII=O bond. Complexes [LnIII(O)(X)2]− (X=NO3− or CH3CO2−; Ln=La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Tm, Lu) are prepared from [LnIII(CH3CO2)(X)3]− precursors through decarboxylation followed by nitromethane or acetone elimination. The oxo complexes hydrolyze at rates indicating LnIII=O bond stability. The rates for [LnIII(O)(NO3)2]− are essentially invariant, whereas those for [LnIII(O)(CH3CO2)2]− exhibit a moderate decrease across the lanthanide series. The kinetics of lanthanide‐oxo bond hydrolysis are assessed in the context of participation of 5d2 electrons in bonding, changes in covalency via variations in 5d orbital energies and radial extensions, and steric crowding around the lanthanide center. The observed fast hydrolysis rates and lack of correlation to electronic and qualitative covalent considerations confirm the expected strong polarization in LnIII=O bonding, with variations in covalency minimally impacting reactivity. The LnIII=O bond reactivity is compared with previous results for LnIII−O⋅ and LnIV=O, and actinide AnIII=O and AnIV=O; implications for lanthanide/actinide and lanthanide/lanthanide partitioning are discussed. Additionally, nitromethane and acetone elimination are demonstrated as useful for inducing a 2e− O‐atom transfer resulting in non‐oxidative formation of lanthanide‐oxos. [ABSTRACT FROM AUTHOR]

The lanthanide (Ln) elements are critical materials that are typically extracted/mined together. Their separation by use of solvent extraction from acidic media is well known; however, there are few studies in basic media with carbonate anions. We investigated the complexation of Eu(III) and Tb(III) carbonates as solids and solutions in alkaline K2CO3, wherein we sought to access a Tb(IV) carbonate complex through ozonolysis. L3‐edge XANES of Eu and Tb carbonate solids, colorless solutions, and a red‐hued Tb solution (obtained by ozonolysis) all showed Ln(III) cations. The absence of evidence for a Tb(IV) complex was confirmed through XAS and EPR analyses, despite the solution exhibiting a deep red color. For solids and solutions, EXAFS results indicate molecular Ln(III)‐carbonato anions. In terms of the Eu(III) carbonate coordination number, the coordination does not change upon dissolution of the solid sample. Furthermore, EXAFS for the solutions revealed evidence for the association of potassium cations with the Ln(III)‐carbonato anions. This direct observation of contact ion pairing by EXAFS at room temperature is rare. The insights into Ln(III) carbonate complexation and solution speciation afforded by XANES‐EXAFS, FT‐IR, and EPR provides perspectives that serve as benchmarks for future computational and experimental efforts focused on caustic‐side solvent extraction of Ln(III) ions. [ABSTRACT FROM AUTHOR]

Background: Rare-earth sulfide nanoparticles (NPs) could harness the optical and magnetic features of rare-earth ions for applications in nanotechnology. However, reports of their synthesis are scarce and typically require high temperatures and long synthesis times. Results: Here we present a biosynthesis of terbium sulfide (TbS) NPs using microorganisms, identifying conditions that allow Escherichia coli to extracellularly produce TbS NPs in aqueous media at 37 °C by controlling cellular sulfur metabolism to produce a high concentration of sulfide ions. Electron microscopy revealed ultrasmall spherical NPs with a mean diameter of 4.1 ± 1.3 nm. Electron diffraction indicated a high degree of crystallinity, while elemental mapping confirmed colocalization of terbium and sulfur. The NPs exhibit characteristic absorbance and luminescence of terbium, with downshifting quantum yield (QY) reaching 28.3% and an emission lifetime of ~ 2 ms. Conclusions: This high QY and long emission lifetime is unusual in a neat rare-earth compound; it is typically associated with rare-earth ions doped into another crystalline lattice to avoid non-radiative cross relaxation. This suggests a reduced role of nonradiative processes in these terbium-based NPs. This is, to our knowledge, the first report revealing the advantage of biosynthesis over chemical synthesis for Rare Earth Element (REE) based NPs, opening routes to new REE-based nanocrystals. [ABSTRACT FROM AUTHOR]

Nanosensitizers having long-lived upconversion emission under near-infrared (NIR) excitation offer unique advantages in terms of reduced background noise and prolonged signal detection for deep tissue therapy of cancer. Herein, we demonstrate a systematic mechanism of energy migration toward achieving long-lived Mn2+ upconversion emission in the multilayered core–shell–shell lattice of NaGdF4:Yb3+,Tm3+,Ca2+/NaGdF4:Yb3+,Ca2+/NaGdF4:Mn2+ upconversion nanoparticles (NPs), following the Yb3+ → Tm3+ → Gd3+ → Mn2+ intermetal ions energy transfer pathway. Furthermore, a rational design of nanosensitizer was achieved by incorporating Er3+ ions into the intermediate shell of multishell NPs, which was subsequently conjugated with the Rose Bengal sensitizer to enable the enhancement in singlet molecular oxygen (1O2) generation under excitation of a 980 nm NIR laser. An intense higher-energy emission in the UV–blue visible region from Tm3+ was achieved by optimizing the amount of Ca2+ in the core–shell NPs, followed by subsequent energy migration to the Mn2+ ion incorporated at the outer shell. The Mn2+ ions were strategically doped in the outer shell of NPs to leverage the catalytic activities of Mn2+ for H2O2 decomposition and decrease the backward energy transfer to the Tm3+ ion. Hence, this approach resulted in a long lifetime of Mn2+ (∼34 ms), attributed to the spin-forbidden 4T1g → 6A1g transition within 3d5 configuration. Additionally, the nanosensitizer demonstrated high 1O2 (∼0.39 μM) generation even at a very low concentration (5 μg/mL) under a laser power of 2 mW cm–2. The hydrogenase-like catalytic activities of Mn2+ exhibited significant oxygen production through decomposition of H2O2. Hence, these findings might contribute to the development of convenient multifunctional nanosensitizers for multimodal bioimaging and therapeutic features, including efficient 1O2 generation and catalytic decomposition of H2O2 (found excessively in a tumor environment) to oxygen for alleviating the hypoxia. [ABSTRACT FROM AUTHOR]

Triple‐stranded helical lanthanide MOFs with CO2 adsorption properties were investigated. Lanthanide MOFs ([Eu0.1Tb0.9(hfa)3(dpa)]n) are composed of lanthanide luminophores (Eu(III) and/or Tb(III) ions), fluorinated antenna ligands (hfa: hexafluoroacetylacetonate), and polyamide‐type linker ligands (dpa: 4‐(diphenylphosphoryl)‐N‐(4‐(diphenylphosphoryl)phenyl)benzamide). The cylindrical structure was characterized by single‐crystal X‐ray analysis, thermogravimetric analysis, and gas adsorption measurements. The inner surfaces of the cylindrical channels were covered with the fluorine atoms of the hfa ligands. The emission intensity ratio (IEu/ITb) in [Eu0.1Tb0.9(hfa)3(dpa)]n is affected by the CO2 gas adsorption behavior. The change in IEu/ITb value was caused by the intermolecular interactions between the CO2 gas molecules and the fluorinated ligands, resulting in an electronic structural change of the lowest triplet excited state in the photosensitized hfa ligands. [ABSTRACT FROM AUTHOR]

The present work elucidates the first report on the synthesis and energy applications of the novel BaLa2MnS5 prepared from single source precursor route. This metal chalcogenide expressed a tuned band gap of 3.84 eV and an average crystallite size of 20.52 nm. Functional groups explored for BaLa2MnS5 expressed strong signals for presence of the metal sulfide bonds. The thermal decomposition pattern of BaLa2MnS5 followed a two‐phased mechanism. Synthesized metal sulfide possessed an irregular morphology with particles arranged in random manner. An assessment of the chalcogenide BaLa2MnS5 for energy applications has been carried out. When employed as an electrode material in 1 M KOH, which acted as the background electrolyte, BaLa2MnS5 chalcogenide showed a specific capacitance of 597 F g−1. Furthermore, this BaLa2MnS5 chalcogenide decorated electrode has a low resistance, as shown by the Rs of 1.35 Ω, and a specific power density of 7366 W kg−1, according to the impedance investigations. The electrochemical results for the OER activity are indicative of the OER overpotential and Tafel slope values as 388 mV and 108 mV/dec. This electrode achieved the HER overpotential value of 241 mV while the obtained Tafel slope was 194 mV/dec. [ABSTRACT FROM AUTHOR]

Molecular and electronic structures of heterobimetallic Ln(III)–Cu(II) C5-symmetric metallamacrocycles (15-metallacrowns-5) bearing L-α-alaninehydroximate (Alaha) ligands are studied by density functional theory (DFT). Full structural DFT optimizations are performed for complexes of the composition {Ln(H2O)4[15-MCCu(II)Alaha-5]}3+ (Ln = La, Ce, Pr) in high- and low-spin states using the PBE functional in the scalar-relativistic approximation. The spin states modeled are: sextet, quartet, and doublet for the La(III)–Cu(II) complex; septet, quintet, triplet, and open-shell singlet for the Ce(III)–Cu(II) complex; octet, sextet, quartet, and doublet for the Pr(III)–Cu(II) complex. The involvement of all unpaired electrons in antiferromagnetic interactions substantially decreases the Gibbs free energy of the singlet Ce(III)–Cu(II) complex compared to that of the doublet La(III)–Cu(II) and Pr(III)–Cu(II) derivatives: –4.4 kcal/mol, –2.0 kcal/mol, and –2.2 kcal/mol respectively (at 5 K). Spin density distributions, electron localization functions (ELFs), and the Laplacian of the electron density in 15-MC-5 reveal Oh and D6h types of the f electron density symmetry around the Ce and Pr nuclei respectively. The effect of the 15-MC-5 metallamacrocyclic environment on the outer electron shell of the central diamagnetic ion is exemplified by the La(III)–Cu(II) complex. The topological parameters of the electron density are calculated at (3, –1) bond critical points for metal–ligand interactions using the quantum theory of atoms in molecules (QTAIM). [ABSTRACT FROM AUTHOR]

Hybrid compounds have a significant impact on agriculture as slow macro- and micronutrient administration systems. This study aimed to evaluate the synthesis and effect of the hybrid compound Nd(NO3)3@Zn-MOF in different concentrations on the in vitro growth of vanilla (Vanilla planifolia Jacks. ex Andrews). A total of 13 vanilla plantlets per treatment were cultivated in test tubes with semi-solid Murashige and Skoog (MS) medium and without growth regulators and treated with 0, 5, 10, 15, and 30 mg L−1 of Nd(NO3)3@Zn-MOF. After 60 days of culture, we evaluated different morphological and biochemical parameters, such as shoot length, root length, the number of roots, the number of leaves, total chlorophyll and carotenoid content, antioxidant capacity, and phenolic compound content. Our results showed that the Nd(NO3)3@Zn-MOF at 10 mg L−1 concentration increased plantlet length. Furthermore, we observed an increase in root length and number with the 5 and 10 mg L−1 concentrations, and a decrease in these same parameters with the 15 and 30 mg L−1 Nd(NO3)3@Zn-MOF concentrations. There were no significant differences regarding the number of leaves or total chlorophyll content. As for the antioxidant capacity, we observed an increase with 5, 10, and 15 mg L−1 of Nd(NO3)3@Zn-MOF and a decrease with the highest concentration. Finally, the phenolic and carotenoid content decreased with the 15 and 30 mg L−1 Nd(NO3)3@Zn-MOF concentrations compared to the control. In conclusion, the hybrid compound Nd(NO3)3@Zn-MOF showed beneficial effects on the growth, physiology, and biochemistry of V. planifolia in vitro when plants were treated at low concentrations. Additionally, the high concentrations used in this study did not induce toxicity. Our findings suggest that Nd(NO3)3@Zn-MOF could be used as a biostimulant in vanilla during its in vitro culture. However, due to the hormetic effect and the possible different reactions of different genotypes, this requires further detailed research. [ABSTRACT FROM AUTHOR]

The sorption of certain lanthanides from aqueous solutions is the focus of this work using antimony oxide (Sb2O5) sorbent. Sb2O5 sorbent was prepared using the precipitation technique, and it has been described using several analytical methods such as Fourier-transformed infrared (FT-IR), X-ray diffraction pattern (XRD), and scanning electron microscope (SEM). The sorption data were collected on Y(III), Ce(III), and Gd(III) including the effects of pH, shaking time, initial metal concentrations, and temperature. The results revealed that saturation capacity has values of (30.6, 27.5, and 24.1 mg/g) for Y(III), Ce(III), and Gd(III), respectively. The sorption of the studied cations is dependent on pH. The reaction kinetics obeyed the pseudo-2nd-order model, and thermodynamics was endothermic and spontaneous. Sorption isotherms are more relevant to a Langmuir isotherm, whose monolayer capacity values are 27.9, 23.2, and 19.8 mg/g for Y(III), Ce(III), and Gd(III), respectively. The real sample applications illustrate the superiority of antimony oxide sorbent in the removal of Y(III), Ce(III), and Gd(III) from high-grade monazite (HGM). [ABSTRACT FROM AUTHOR]

Developing highly stable and efficient catalysts for oxygen evolution reaction (OER) is extremely important to sustainable energy conversion and storage, but improved efficiency is largely hindered by sluggish reaction kinetics. Dense and bimetal ruthenates have emerged as one of the promising substitutes to replace single-metal ruthenium or iridium oxides, but the fundamental understanding the role of A-site cations is still blurring. Herein, a family of lanthanides (Ln = all the lanthanides except Pm) are applied to synthesize pyrochlore lanthanide ruthenates (Ln2Ru2O7), and only Ln2Ru2O7 (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu) with pure phase can be obtained by the ambient-pressure calcination. Compared with the perovskite ruthenates (SrRuO3) and rutile RuO2, the [RuO6] units in these Ln2Ru2O7 present the largely distorted configurations and different energy level splitting to prevent the excessive Ru oxidation and dissolution, which leads the primary improvement in the electrocatalytic OER performance. In the similar crystalline field split states, the charge transfer between [RuO6] units and Ln3+ cations also affect catalytic activities, even in the Ln2Ru2O7 surface reconstruction during the OER process. Consequently, Tb2Ru2O7 showed the highest OER performance among all the prepared Ln2Ru2O7 with similar morphologies and crystallization. This systematic work gives fundamental cognition to rational design of high-performance OER electrocatalysts in proper water electrolysis technologies.

We evaluated the effects of neodymium (0.000, 2.885, 5.770 and 8.655 mg · L−1) and zinc (0.1, 0.2 and 0.3 mg · L−1), as well as their interaction on lettuce plants in hydroponics. Applications of 2.885 mg Nd · L−1 and 5.770 mg Nd · L−1 increased plant height, number of leaves and leaf area, as well as fresh and dry stem, root and total biomasses. Root volume was greater in plants treated with 2.885 mg Nd · L−1. With 0.1 mg Zn · L−1, plant height, leaf area and fresh stem, root and total biomass were greater, while applying 0.3 mg Zn · L−1 increased the ratio of dry biomass of stems and roots. Plants exposed to 5.770 mg Nd · L−1 + 0.3 mg Zn · L−1 exhibited greater leaf length. The ratios of fresh and dry biomass of stems and roots increased in plants treated with 8.655 mg · L−1 Nd + 0.3 mg Zn · L−1. Dry biomass weights of stems, roots and total were the highest in plants treated with 20 mg Nd · L−1 + 0.1 mg Zn · L−1. Nd significantly increased foliar concentration of N, P and K. Hence, Nd and Zn improve growth and nutrition.

Abstract Background Rare-earth sulfide nanoparticles (NPs) could harness the optical and magnetic features of rare-earth ions for applications in nanotechnology. However, reports of their synthesis are scarce and typically require high temperatures and long synthesis times. Results Here we present a biosynthesis of terbium sulfide (TbS) NPs using microorganisms, identifying conditions that allow Escherichia coli to extracellularly produce TbS NPs in aqueous media at 37 °C by controlling cellular sulfur metabolism to produce a high concentration of sulfide ions. Electron microscopy revealed ultrasmall spherical NPs with a mean diameter of 4.1 ± 1.3 nm. Electron diffraction indicated a high degree of crystallinity, while elemental mapping confirmed colocalization of terbium and sulfur. The NPs exhibit characteristic absorbance and luminescence of terbium, with downshifting quantum yield (QY) reaching 28.3% and an emission lifetime of ~ 2 ms. Conclusions This high QY and long emission lifetime is unusual in a neat rare-earth compound; it is typically associated with rare-earth ions doped into another crystalline lattice to avoid non-radiative cross relaxation. This suggests a reduced role of nonradiative processes in these terbium-based NPs. This is, to our knowledge, the first report revealing the advantage of biosynthesis over chemical synthesis for Rare Earth Element (REE) based NPs, opening routes to new REE-based nanocrystals.

The mode of action, bioaccumulation potential and toxicity of Rare Earth Elements (REE), with several applications in the technology, medical and agricultural fields, are still understudied. The nitrates acute effects on single exposures, binary and ternary mixtures of lanthanum (La), neodymium (Nd) and samarium (Sm) on Lactuca sativa lettuce seed germination and wet biomass in an artificial soil (AS) and an Ultisol were assessed. Germination (EC50), wet biomass (IC50) and germination inhibition (% GI) were evaluated. EC50 values show La was the most toxic in Ultisol, Sm in AS, and Nd appears with intermediate values on both substrates. The IC50, both single and mixed, decreased from 3- to 181-fold with increasing test concentrations in relation to the control in AS, while increases in Ultisol were observed, followed by decreases at higher doses which may be associated with the low-dose stimulation effect (hormesis). Our findings may be used to subsidize REE risk assessment studies and reinforce the hormesis effect to prevent the use of high application of REE fertilizers, avoiding the accumulation of REE in agricultural soils. [ABSTRACT FROM AUTHOR]

Biomolecular aggregates ensure the optimum concentration and proximity required for biochemical processes to take place. Synthetic aggregating systems are becoming increasingly essential to study/mimic dynamic condensates in nature. Herein the ratiometric DNA aggregation of self‐assembled DNA constructs using lanthanide salts is reported. In addition, the aggregation is shown to be reversed by the addition of specific lanthanide‐binding ligands. The aggregate formation is confirmed by dynamic light scattering experiment, electrophoretic mobility shift assay, and field emission scanning electron microscope. This programmed DNA aggregation and its reversion are applied to evaluating the lanthanide‐DNA and lanthanide‐ligand binding constants, respectively. To achieve this, Forster resonance energy transfer (FRET) pair dyes at the 3′ or 5′ end of the DNA strands are strategically placed that generate unique fluorescence patterns upon interaction with the DNA constructs and different triggers such as lanthanides/ligands/monovalent cations, thus enabling the tracking of various states of binding. It also demonstrates a “fast method” to form and stabilize G‐quadruplex (GQ) using lanthanides which complements the existing slow formation of GQs with Na+/K+ ions. The formation of GQ by lanthanides is corroborated by FRET, circular dichroism (CD), and enzyme linked immunosorbent assay (ELISA) experiments. These DNA constructs, formed by lanthanides, have shown resistance to cleavage by DNase I, and distinctive binding to Protoporphyrin dyes and Thioflavin T. [ABSTRACT FROM AUTHOR]

Large dissymmetry factor of the circularly polarized luminescence (gCPL) was observed in ligand and coordination tuned chiral tetrakis europium (Eu(III)) complexes with ammonium cations. The gCPL value was estimated to be −1.54, which is the largest among chiral luminescent molecules. Through photophysical measurements, single crystal X‐ray structural analyses and quantum chemical calculations, changes in the geometric and electronic structures were observed for a series of chiral tetrakis Eu(III) complexes which enhanced the gCPL value. The emission quantum yield and photosensitized energy transfer efficiencies of chiral Eu(III) complexes with ammonium cations were also larger than those of chiral Eu(III) complex with Cs+. Based on the systematic modifications and analyses for chiral tetrakis Eu(III) complex, effect of the ammonium cation on enhanced CPL brightness is reported. [ABSTRACT FROM AUTHOR]

Sandwich d/f heterometallic complexes [(Ln(hfac)3)2M(acac)3] (Ln = La, Pr, Sm, Dy and M = Co; Ln = La and M = Ru) were prepared in strictly anhydrous conditions reacting the formally unsaturated fragment [Ln(hfac)3] and [M(acac)3] in a 2-to-1 molar ratio. These heterometallic complexes are highly sensitive to moisture. Spectroscopic observation revealed that on hydrolysis, these compounds yield dinuclear heterometallic compounds [Ln(hfac)3M(acac)3], prepared here for comparison purposes only. Quantum mechanical calculations supported, on the one hand, the hypothesis on the geometrical arrangement obtained from ATR-IR and NMR spectra and, on the other hand, helped to rationalize the spontaneous hydrolysis reaction. [ABSTRACT FROM AUTHOR]

Eu/Tb metal–organic frameworks (Eu/Tb-MOFs), exhibiting Eu3+ and Tb3+ emissions, stand out as some of the most fascinating luminescent thermometers. As the relative thermal sensitivity model is limited to its lack of precision for fitting ratio of Eu3+ and Tb3+ emissions, accurately predicting the sensing performance of Eu/Tb-MOFs remains a significant challenge. Herein, we report a series of luminescent Eu/Tb-MOF thermometers, EuxTb1−xL, with excellent thermal sensitivity around physiological levels, achieved through the tuning energy transfer from ligands to Eu3+ and Tb3+ and between the Ln ions. It was found that the singlet lowest-energy excited state (S1) of the ligand and the higher triplet energy level (Tn) are crucial in the energy transfer processes of ligand→Tb3+ and ligand→Eu3+. This enables EuxTb1−xL to serve as an effective platform for exploring the impact of these energy transfer processes on the temperature-sensing properties of luminescent Eu/Tb-MOF thermometers. The relative thermal sensitivity is comparable to that of dual-center MOF-based luminescent thermometers operating at physiological levels. This study provides valuable insights into the design of new Eu/Tb thermometers and the accurate prediction of their sensing performance. [ABSTRACT FROM AUTHOR]

Recently, lanthanide‐based 0D metal halides have garnered considerable attention owing to their applications in light–emitting diodes (LEDs), X‐ray imaging, and photodetectors. Among these materials, 0D Cs3TbCl6 (CTC) nanocrystals (NCs) have demonstrated promising performance in X‐ray imaging and light‐emitting diodes. However, a considerable drawback of CTC NCs is their limited absorption coefficient in the UV‐A region (315–380 nm). To address this limitation and enhance the absorption coefficient in the UV‐A region, Ce3+ is incorporated into CTC NCs—advantageous owing to the high absorption coefficient of Ce3+ in the UV‐A region, attributed to—4f‐5d orbital coupling. In addition, Ce3+ ions sensitize the luminescence of CTC NCs and enhance the photoluminescence quantum yield from 75% to 87%. Energy transfer from Ce3+ to Tb3+ is investigated at different dopant ratios. Furthermore, Cs3CeTbCl6 (CCTC) NCs have been utilized in white LED devices. Understanding such competitive energy transfer in lanthanide‐based perovskite‐inspired metal halides will facilitate the development of novel luminescent metal halides for lighting applications. [ABSTRACT FROM AUTHOR]

Molecular scaffolds are ideal for investigating upconversion (UC) at the highest spatial resolution and to create precisely controllable luminescent materials. Such control may be the key to overcoming the limitations of brightness and reproducibility found in UC micro‐ and nanoparticles. Cooperative UC can significantly increase luminescence brightness and bulk studies showed that highest efficiencies can be obtained by sensitizer‐to‐activator ion ratios ≥ 2, that is, via high probabilities of sensitizing the emitting lanthanide ion. Using nonanuclear molecular complexes, the authors demonstrate both experimentally and theoretically that interion distances are more relevant and that the highest UC efficiencies are actually attained for sensitizer‐to‐activator ion ratios around 1. By modeling accretive and cooperative sensitization UC, energy migration, and fitting experimental data, it is revealed that cooperative sensitization is predominant for the determination of UC luminescence intensities, whereas energy migration defines UC luminescence kinetics. The implementation of interion distances and different energy transfer mechanisms into advanced modeling of experimental UC data will be paramount for designing brighter and better UC materials. [ABSTRACT FROM AUTHOR]

The Mandorla di Avola is recognized all over the world as one of the best almond varieties. It is cultivated in a small area inside the provinces of Siracusa and Ragusa (Sicily, southern Italy). It is used in traditional Sicilian cuisine for both salty and sweet foods and of course in artisan pastry, apart from being consumed as a fruit. Due to its extraordinary organoleptic and beneficial features, the Mandorla di Avola is frequently counterfeit with almond varieties of lower quality coming from other countries. While its nutraceutical features have been studied, the possibility of authenticating it with respect to other varieties has not been explored. In this work, we used microelements determined with ICP-OES and ICP-MS as chemical descriptors to distinguish samples of Mandorla di Avola almonds from almonds coming from California and Spain, which are usually employed as substitutes in pastry. Among the different elements determined, Mn and P were found to be the best descriptors for authentication. [ABSTRACT FROM AUTHOR]

Many bacteria secrete metallophores, low-molecular-weight organic compounds that bind ions with high selectivity and affinity, in order to access essential metals from the environment. Previous work has elucidated the structures and biosynthetic machinery of metallophores specific for iron, zinc, nickel, molybdenum, and copper. No physiologically relevant lanthanide-binding metallophore has been discovered despite the knowledge that lanthanide metals (Ln) have been revealed to be essential cofactors for certain alcohol dehydrogenases across a diverse range of phyla. Here, we report the biosynthetic machinery, the structure, and the physiological relevance of a lanthanophore, methylolanthanin. The structure of methylolanthanin exhibits a unique 4-hydroxybenzoate moiety which has not previously been described in other metallophores. We find that production of methylolanthanin is required for normal levels of Ln accumulation in the methylotrophic bacterium Methylobacterium extorquens AM1, while overexpression of the molecule greatly increases bioaccumulation and adsorption. Our results provide a clearer understanding of how Ln-utilizing bacteria sense, scavenge, and store Ln; essential processes in the environment where Ln are poorly bioavailable. More broadly, the identification of this lanthanophore opens doors for study of how biosynthetic gene clusters are repurposed for additional functions and the complex relationship between metal homeostasis and fitness. [ABSTRACT FROM AUTHOR]

Supramolecular adducts of lanthanide complexes with cucurbituril, [{Eu(1–x)Nd(1+x)(H2O)5(NO3)}2 CB[6]](NO3)4·HNO3·6H2O (x = 0.5, –0.5), are prepared by heating a mixture of dissolved lanthanide nitrates and cucurbit[6]uril. According to the single-crystal XRD data for 1 and 2, the metal is connected to the macrocycle through the bidentate coordination of oxygen atoms of cucurbit[6]uril portals to the lanthanide(III) cations, thus leading to the formation of a molecular complex. In the crystal, the [{Ln(H2O)5(NO3)}2(CB[6])]4+ cations are interconnected by a system of hydrogen bonds. The compounds are shown to be isostructural and are characterized by a number of physicochemical methods: IR spectroscopy, powder XRD, and elemental analysis. Their luminescence spectra are recorded. [ABSTRACT FROM AUTHOR]

Isostructural binuclear complexes [Ln2L2(hfac)6] (Ln = Eu, Tb; hfac– = hexafluoroacetylacetonate ion) are synthesized by the interaction of [Ln(hfac)3(H2O)2] with 3,6-bis(diphenylphosphinyl)pyridazine (L). According to the single-crystal XRD data, two Ln(hfac)3 moieties in the complexes are connected by two O,O´-bidentate-bridging ligands L, and the coordination polyhedron Ln@O8 has the geometry of a triangular dodecahedron. The Eu3+ and Tb3+ complexes exhibit characteristic lanthanide-centered photoluminescence in the solid state at 297 K with luminescence quantum yields of 31% and 2% and excited state lifetimes of 707 and 30 μs, respectively, thus indicating that luminescence sensitization by the ligand environment is more effective for Eu3+ than for Tb3+. [ABSTRACT FROM AUTHOR]

Polysaccharides are widely represented in plants and bacteria, where they are distinguished by their extraordinary structural diversity and the performance of various functions. To study the functions of polysaccharides, their fluorescent labeling is needed. This review discusses methods for introducing fluorescent labels into polysaccharides by chemical modification of certain functional groups of these complex biopolymers, as well as using the so-called bioorthogonal reactions, which allow labeling in a cell without affecting its viability. In addition to modification with organic dyes, the possibility of using quantum dots and coordination compounds of lanthanides is also discussed. [ABSTRACT FROM AUTHOR]

Lanthanides and actinides are emerging contaminants, but little is known about their uptake and distribution by plants and their interactions in the rhizosphere. To better understand the fate of these metals in plants, the bioassociation of 2, 20 and 200 µM Eu(III) by five hydroponically grown crops endemic to Europe was assessed. The metal's concentration and its speciation were monitored by inductively coupled plasma mass spectrometry and laser spectroscopy, whereas root exudation was investigated by chromatographic methods. It has been shown, that Eu(III) bioassociation is a two-stage process, involving rapid biosorption followed by accumulation in root tissue and distribution to the stem and leaves. Within 96 h of exposure time, the plant induces a change of Eu(III) speciation in the liquid medium, from a predominant Eu(III)aquo species, as calculated by thermodynamic modelling, to a species with longer luminescence lifetime. Root exudates such as citric, malic, and fumaric acid were identified in the cultivation medium and affect Eu(III) speciation in solution, as was shown by a change in the thermodynamic model. These results contribute to a comprehensive understanding of the fate of lanthanides in the biosphere and provide a basis for further investigations with the chemical analogues Cm(III) and Am(III). [ABSTRACT FROM AUTHOR]

The study of ytterbium halide crystals using the compound-tunable embedding potential (CTEP) method is carried out in the framework of the density functional theory. For subsequent calculations the optimization of atomic bases is carried out, and for this purpose stoichiometric molecular systems were studied, using the coupled-cluster methods. The chemical shift of the lines of the X-ray emission spectrum, Kα1 and Kα2, in YbHal3 relative to YbHal2 was chosen as a criterion for verifying the computational accuracy of the properties localized on the nucleus of a heavy atom, Yb, since this method is a unique tool for analyzing partial electron densities near a heavy nucleus specifically for compounds of d- and f-elements. In the study, five main versions for the halogen basis set sizes were considered. The stability of the results was obtained using the CCSD and CCSD(T) coupled cluster methods for molecular systems YbF2, YbF3, YbCl2 and YbCl3. [ABSTRACT FROM AUTHOR]

Lanthanide nanoparticle (LnNP) scintillators exhibit huge potential in achieving radionuclide‐activated luminescence (radioluminescence, RL). However, their structure–activity relationship remains largely unexplored. Herein, progressive optimization of LnNP scintillators is presented to unveil their structure‐dependent RL property and enhance their RL output efficiency. Benefiting from the favorable host matrix and the luminescence‐protective effect of core–shell engineering, NaGdF4 : 15 %Eu@NaLuF4 nanoparticle scintillators with tailored structures emerged as the top candidates. Living imaging experiments based on optimal LnNP scintillators validated the feasibility of laser‐free continuous RL activated by clinical radiopharmaceuticals for tumor multiplex visualization. This research provides unprecedented insights into the rational design of LnNP scintillators, which would enable efficient energy conversion from Cerenkov luminescence, γ‐radiation, and β‐electrons into visible photon signals, thus establishing a robust nanotechnology‐aided approach for tumor‐directed radio‐phototheranostics. [ABSTRACT FROM AUTHOR]

Remote thermal sensing has emerged as a temperature detection technique for tasks in which standard contact thermometers cannot be used due to environment or dimension limitations. One of such challenging tasks is the measurement of temperature in microelectronics. Here, optical thermometry using co-doped and mixed dual-center Gd2O3:Tb3+/Eu3+ samples were realized. Ratiometric approach based on monitoring emission intensities of Tb3+ (5D4–7F5) and Eu3+ (5D0–7F2) transition provided sensing in the range of 30 °C–80 °C. Dispersion system type only slightly affected relative sensitivity, accuracy and precision. The applicability of phosphors synthesized to be utilized as remote optical thermometers for microelectronics has been proved with an example on a surface mount resistor and microcontroller. [ABSTRACT FROM AUTHOR]

Crystallophores are lanthanide complexes that have demonstrated outstanding induction of crystallization for various proteins. This article explores the effect of tailored modifications of the crystallophore first generation and their impact on the nucleating properties and protein crystal structures. Through high‐throughput crystallization experiments and dataset analysis, we evaluated the effectiveness of these variants, in comparison to the first crystallophore generation G1. In particular, the V1 variant, featuring a propanol pendant arm, demonstrated the ability to produce new crystallization conditions for the proteins tested (hen‐egg white lysozyme, proteinase K and thaumatin). Structural analysis performed in the case of hen egg‐white lysozyme along with Molecular Dynamics simulations, highlights V1′s unique behavior, taking advantage of the flexibility of its propanol arm to explore different protein surfaces and form versatile supramolecular interactions. [ABSTRACT FROM AUTHOR]

Novel 1-phenyl(1-thiophen-2-yl)-4-(diphenylphosphoryl)butane-1,3-diones were synthesized by the Claisen-type condensation of 1-(diphenylphosphoryl)propan-2-one with ethyl phenyl(thiophene-2-yl)carboxylates. The tautomeric equilibrium of diketone moiety of phosphine oxides was investigated by 1H and 13C{1H} NMR spectroscopy. Two species out of five possible tautomers (diketo and mono-enol) were observed in the solution of 1-phenyl(1-thiophen-2-yl)-4-(diphenylphosphoryl)butane-1,3-diones. The major tautomer was the mono-enol form with content 80–90%. Furthermore, the double bond position at C3 atom was determined by 13C{1H} NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Lanthanoid carboxylates were synthesized and in situ self‐assembled to illustrate temperature‐driven evolution in chromaticity. Evolution in structure (crystallinity), composition, luminosity, and chromaticity were investigated revealing the coupled role of divergence in order/structure (spatial organization), and composition in tuning observed color. Loss of crystallinity or increase in residual carbon leads to decrease in luminosity even with increase in hue. Comparing Ho and Er congeners shows that the density of accessible transition states relates to shifts in low and high wavelength components of color. This work demonstrates that, just as interface dipoles can lead to change in semiconductor band gap, structure and composition can analogously alter observed color. [ABSTRACT FROM AUTHOR]

Rare earth elements (REE) are vital for powerful permanent magnets used in electric motors and wind turbines. These elements are chiefly sourced from carbonatites and their weathering products. The economic attractiveness of carbonatites is explained by the 10,000‐fold enrichment of REE in their mineralized portions relative to the average continental crust. Carbonatites form from mantle‐derived melts, but the ultimate origin of their REE is not completely clear. One widely cited model invokes subduction of marine sediments which accumulate REE‐rich material, priming the mantle to produce REE‐rich carbonatite melts which subsequently form deposits in the upper crust. Here we examine a global marine sediment compilation, revealing a wide variety in REE abundances and patterns. We use the sensitive lambda method that separates REE pattern curvature from redox‐related element anomalies to examine both marine sediments and presumably derived carbonatite rocks. We find that the most REE‐rich marine sediments are characterized by strongly negative Ce anomalies, which if recycled via subduction, mineralized carbonatites are expected to inherit. In contrast, we find that mineralized carbonatite rocks do not contain Ce anomalies. This indicates that the REE from the most REE‐rich marine sediments are not recycled into carbonatite deposits, and a different REE source is needed to explain carbonatite fertilities. We also find evidence that raises questions on whether any sediment‐derived REE are present in carbonatite deposits to a significant amount. We suggest that a REE‐rich source may not be required and REE enrichment occurs primarily during crustal magmatic differentiation. Plain Language Summary: Rare earth elements (REE) such as neodymium are important components of permanent magnets used in energy generation technologies including wind power turbines and electric motors. These metals are extracted from carbonatite rocks, but how the REE got to carbonatites in the first place is contentious. The seafloor contains accumulations of exceptionally REE‐rich sediments, and a popular model proposes that these REE are recycled to the mantle during subduction. Once melting occurs in the mantle, these same REE are suggested to be transported in the carbonatite melts and eventually reach the upper crust where they contribute to economic mineralization. However, the REE‐rich sediments contain a ubiquitous chemical signature in the form of a redox‐sensitive negative cerium anomaly. We show that the anomaly does not occur in carbonatite rocks, with the implication that recycled REE‐rich sediments cannot necessarily be the source for carbonatite‐related ore deposits. Key Points: Subducted REE‐rich sediments with negative Ce anomalies are thought to supply carbonatites with their REECarbonatites have no statistically significant negative Ce anomalyRecycling of particularly REE‐rich marine sediments not required for mineralization [ABSTRACT FROM AUTHOR]

Compounds of three types, [LnL3(C2H5OH)] (Ln = Nd (I), Sm (II), Eu (III)), [LnL3(H2O)] (Ln = Gd (IV), Tb (V)), and [DyL2(NO3)(C2H5OH)2] (VI), were obtained by reactions of lanthanide nitrate with NaL (L– = 2,4-dichlorophenoxyacetate anion) in ethanol. The composition and structure of complexes I–VI were investigated by elemental and thermogravimetric analysis, IR spectroscopy, and X-ray diffraction (nos. 2311578 (I), 2311579 (II), 2311580 (III), 2311581 (IV), 2311582 (VI)). All compounds have a one-dimensional polymer structure in which metal atoms are connected by bridging carboxylate groups. The π–π interactions and intermolecular contacts between the chains give rise to a three-dimensional supramolecular structure. [ABSTRACT FROM AUTHOR]

The presence of the olive tree in Tuscany, Italy, in its forms that have survived to the present day as an essential component of the landscape dates back many centuries. Global change is now threatening it. Therefore, it is important to find markers to enhance the olive tree environment in terms of its resilience. The aim of the research was to investigate the composition of soil bacteriomes in contrasting geochemical environments using a geochemistry approach based on the behavior of the REEs, inherited from parent rock material. Bacteriome assemblages and REE content were analyzed in 48 topsoils developed in six geochemical Tuscan environments. Combined geochemical, geoinformatic, and bioinformatic techniques highlighted the existence of four bacteriome assemblages depending on Light-REEs. Further results showed that the soil bioavailable fraction of REEs was related to parent rock materials, pH, and bacteriome composition. The most abundant bacteria were Microlunatus in graded fluvio-lacustrine soils, Gaiella in graded arenaceous soils, Bradyrizhobium in pyroclastic soils, and Rubrobacter in soils on gentle slopes of calcareous and carbonatic lithologies. This research represents a starting point to define new indicators able to assess the resilience of the olive trees in the Mediterranean landscape and characterize the territory of extra virgin olive oils. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis and characterization of rare-earth-metal complexes using ligands that adhere to the CHON principle. The complexes were studied using various spectroscopic and electrochemical techniques, as well as computational studies. The tren-based ligands showed lower ion pairing compared to their SP-analogues, and exhibited a greater propensity to complex with lutetium. Selectivity studies showed that the ligands favored complexation with lutetium and samarium, and py3tren was found to be the most selective ligand. The research aims to contribute to the development of sustainable solutions for nuclear waste management. [Extracted from the article]

The synthesis of lanthanide‐based organometallic sandwich compounds is very appealing regarding their potential for single‐molecule magnetism. Here, it is exploited by on‐surface synthesis to design unprecedented lanthanide‐directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six‐membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X‐ray absorption spectroscopy, X‐ray linear and circular magnetic dichroism, and X‐ray photoelectron spectroscopy, complemented by density functional theory‐based calculations. Both lanthanide complexes self‐assemble in close‐packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self‐assembly, the erbium‐based species is magnetically isotropic, whereas the dysprosium‐based compound features an in‐plane magnetization. [ABSTRACT FROM AUTHOR]

A series of CoIII–LnIII–CoIII trinuclear complexes [Ln{Co(Hmtimn)3}2](NO3)3 were prepared by following a simple one-pot synthesis method, mixing an unsymmetrical bidentate ligand 2-(2-imidazolinyl)-6-methoxypheol (H2mtimn) with Co(NO3)2·6H2O and LnX3· 6H2O (where Ln = La, Ce, Pr, Nd, Gd or Dy and X = NO3− or Cl−) in methanolic solution in the presence of triethylamine in air. In the reaction mixture, this leads to the in situ formation of a tris-chelate CoIII metalloligand unit, which can coordinate LnIII ions through the interactions of phenolato- and methoxy-O donors. X-ray structural analysis revealed that the CoIII metalloligand functions as a rigid tripodal ligand to coordinate to a LnIII ion by six oxygen donors. The two metalloligands in the complex exhibit homochiral aggregation (ΔΔ or ΛΛ) upon coordination to the LnIII ion. The coordination of the central LnIII ion was found to be a distorted icosahedral geometry. Magnetic susceptibility measurements reveal that both cobalt and central lanthanide ions exist in trivalent states. [ABSTRACT FROM AUTHOR]

Pb2+ codoping enhances the Tb3+ emission in trivalent terbium-doped zinc sulfide [Zn-(Tb)-S] nanoparticles (NPs). The Tb3+-Pb2+ spatial proximity and a favorable codopant electronic energy level alignment contribute toward this emission brightening. This work tests the performance of the Tb3+ emission in the Zn-(TbPb)S and Zn-(Tb)-S/Pb NPs, where the dopants within parentheses and after slashes indicate their synthetic and postsynthetic doping, respectively. When screened against steady-state and time-resolved photoluminescence, photoelectron spectroscopy, zeta potential, and infrared absorption of surface capping ligands, the Zn-(TbPb)S NPs emerge as a superior sensitizer to generate Tb3+ emission. A core dominant Tb3+-Pb2+ interaction in Zn-(TbPb)S NPs prompts a stronger Tb3+ emission when compared to the surface dominant Tb3+-Pb2+ interaction in Zn-(Tb)-S/Pb NPs. This doping strategy guided the NP design principle to control lanthanide emission, which expands the palette of lanthanide-based NP luminophores for practical applications. The Pb2+‑sensitized Tb3+ emission brightening in the ZnS NPs in the precation exchange reaction conditions can find applications in Pb2+ sensing, cellular imaging, and light emitting diodes (LEDs). [ABSTRACT FROM AUTHOR]

This study is focused on determining the refractive index as a crucial parameter for evaluating the intrinsic quantum yield and the ligand sensitisation efficiency in solid‐state trivalent lanthanide coordination compounds. For this, eight trivalent europium complexes with phenyl‐terpyridine ([EuX3(ptpy)(L)], X=Cl− or NO3−, ptpy=4′‐phenyl‐2,2′ : 6′,2′′‐terpyridine, L=H2O or other molecules) were examined. Their refractive indices were determined using the Becke lines test by immersing transparent material in a series of media with known refractive indices. Using the set of media presented here, determining crystalline materials′ refractive indices from 1.41 to 1.73 with a step of 0.01 is possible. Assessment of the refractive indices of the complexes mentioned above allowed a comprehensive analysis of their photophysical properties in the solid state. Moreover, this method can be extrapolated for other solid‐state materials, offering valuable insights in the broader field of photophysics. In addition to photoluminescence investigations, the compounds presented were characterised by single‐crystal X‐ray diffraction (SCXRD), powder X‐ray diffraction (PXRD), Hirschfeld surface area analysis, UV‐Vis reflectance spectroscopy, hydrolysis sensitivity analysis, and simultaneous thermogravimetry and differential thermal analysis coupled with mass‐spectrometry (STA‐MS). [ABSTRACT FROM AUTHOR]