Lanthanide-Doped ZnO Nanoparticles: Unraveling Their Role in Cytotoxicity, Antioxidant Capacity, and Nanotoxicology.

This study used a sonochemical synthesis method to prepare (La, Sm)-doped ZnO nanoparticles (NPs). The effect of incorporating these lanthanide elements on the structural, optical, and morphological properties of ZnO-NPs was analyzed. The cytotoxicity and the reactive oxygen species (ROS) generation capacity of ZnO-NPs were evaluated against breast (MCF7) and colon (HT29) cancer cell lines. Their antioxidant activity was analyzed using a DPPH assay, and their toxicity towards Artemia salina nauplii was also evaluated. The results revealed that treatment with NPs resulted in the death of 10.559-42.546% and 18.230-38.643% of MCF7 and HT29 cells, respectively. This effect was attributed to the ability of NPs to downregulate ROS formation within the two cell lines in a dose-dependent manner. In the DPPH assay, treatment with (La, Sm)-doped ZnO-NPs inhibited the generation of free radicals at IC50 values ranging from 3.898 to 126.948 µg/mL. Against A. salina nauplii, the synthesized NPs did not cause death nor induce morphological changes at the tested concentrations. A series of machine learning (ML) models were used to predict the biological performance of (La, Sm)-doped ZnO-NPs. Among the designed ML models, the gradient boosting model resulted in the greatest mean absolute error (MAE) (MAE 9.027, R2 = 0.86). The data generated in this work provide innovative insights into the influence of La and Sm on the structural arrangement and chemical features of ZnO-NPs, together with their cytotoxicity, antioxidant activity, and in vivo toxicity.

Luminescent lanthanide mixed N-phthaloylglycinate and terephthalate coordination polymers: Structural and optical properties.

A new class of lanthanide mixed-carboxylate ligands compounds with formula {[Ln2 (phthgly)4 (bdc)(H2 O)6 ]·(H2 O)4 }∞ , labelled as Ln3+ : Eu (1) and Gd (2) coordination polymers (CP) were synthesized under mild reaction conditions between lanthanide nitrate salts and a solution of N-phthaloylglycine (phthgly) and terephthalic (bdc) ligands. The (1) and (2) coordination polymers were formed by symmetric binuclear units, in which phthgly and bdc carboxylate ligands are coordinated to the lanthanide ions by different coordination modes. Surprisingly, all organic ligands participate in hydrogen bonding interactions, forming an extremally rigid crystalline structure. The red narrow emission bands from the 5 D0 →7 FJ transitions of the Eu3+ ion show a high colour purity. The intramolecular energy transfer process from L→Eu3+ ion has been discussed. The experimental intensity parameters (Ω2,4 ) reflect lower angular distortion and polarizability of the chemical environment around the metal ion compared with other Eu3+ compounds reported in the literature. This novel class of coordination polymer offers a more attractive platform for developing luminescent functional materials for different applications.

A combined experimental-molecular modeling study of crown ether europium complexes: Effects of the coordinated anion on structural and luminescence properties.

It is reported the synthesis, characterization by elemental analysis, thermogravimetry; electronic absorption, infrared, excitation, and emission spectroscopies of the [Eu(12C4)(phen)2(X)n]X2 complexes, where 12C4 = 12-crown-4, phen = 1,10-phenanthroline, and X  = F-, Cl-, Br-, SCN-, ClO4-, and NO3-. It is verified that the polarizability of the anion X- exerts remarkable effects on the emission process. As a general trend, lower wavenumbers for the 7F0→5L6, 7F0→5D2 and 7F0→5D1 transitions are associated with the anions with higher volumes and, consequently, higher polarizability. The molecular modeling results performed with quantum methods (RHF and DFT) suggest some relationships between the calculated structures, electronic, and luminescence properties with the presence of the LMCT (ligand-to-metal charge transfer) states, which explains the differences in the emission spectra of these complexes due to the coordinated anion.

Synthesis, solid state characterization, theoretical and experimental spectroscopic studies of the new lanthanide complexes.

Three new complexes Na[Ln(pic)4]ּ⋅2.5H2O (Ln = Tb, Eu or Gd; pic = picolinate) were synthesized and characterized by infrared spectroscopy, powder X-ray diffraction and thermogravimetric analyses. The molecular structures of the complexes have been determined by single-crystal X-ray diffraction. The three isostructural lanthanide complexes crystalize in the hexagonal system with space group P6122 to Eu complex and Gd complex and space group P6522 to Tb complex. In each of the complexes, the picolinate ligands are bonded to Ln3+ and Na+ ions by different coordination modes promoting polymeric structures. The photoluminescent properties of complexes were studied and combined with theoretical studies using the density functional theory (DFT: B3LYP, PBE1PBE) and the semiempirical method AM1/Sparkle from the single crystal X-ray diffraction structures to assign a suitable model for describing the system. The B3LYP DFT functional was considered the most adequate for providing structural properties of the compounds and for describing luminescence properties. The excited triplet states (T1) and excited singlet states (S1) of the ligand were determined theoretically using Time-dependent DFT calculations (TD-DFT: B3LYP, CAM-B3LYP and LC-wPBE) and INDO/S-CIS, with the best agreement with experimental values obtained from the LC-wPBE DFT functional. The photoluminescent spectra of the complexes and their lifetime measurements were determined indicating that the Eu complex and Tb complex display different intramolecular energy transfer mechanisms with higher efficiency to ligand-to-terbium energy transfer. In addition, the experimental and theorical Judd-Ofelt intensity parameters and quantum yields of the complexes were also determined and discussed besides to a proposed 9-state diagram to describe the luminescence properties of the Eu complex. The low value of emission quantum efficiency of 5D0 emitting level of Eu(III) ion was explained by the presence of the ligand-to-metal charge transfer state (LMCT) evidenced experimentally and theoretically. A good agreement was obtained between the proposed kinetic model and experimental results showing the consistency of the set of rate equations assumed and the intramolecular pathways proposed.

Effect of Doping TiO2 NPs with Lanthanides (La, Ce and Eu) on the Adsorption and Photodegradation of Cyanide-A Comparative Study.

Free cyanide is a highly dangerous compound for health and the environment, so treatment of cyanide-contaminated water is extremely important. In the present study, TiO2, La/TiO2, Ce/TiO2, and Eu/TiO2 nanoparticles were synthesized to assess their ability to remove free cyanide from aqueous solutions. Nanoparticles synthesized through the sol-gel method were characterized by X-ray powder diffractometry (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier-transformed infrared spectroscopy (FTIR), diffuse reflectance spectroscopy (DRS), and specific surface area (SSA). Langmuir and Freundlich isotherm models were utilized to fit the adsorption equilibrium experimental data, and pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to fit the adsorption kinetics experimental data. Cyanide photodegradation and the effect of reactive oxygen species (ROS) on the photocatalytic process were investigated under simulated solar light. Finally, reuse of the nanoparticles in five consecutive treatment cycles was determined. The results showed that La/TiO2 has the highest percentage of cyanide removal (98%), followed by Ce/TiO2 (92%), Eu/TiO2 (90%), and TiO2 (88%). From these results, it is suggested that La, Ce, and Eu dopants can improve the properties of TiO2 as well as its ability to remove cyanide species from aqueous solutions.

Antileishmanial Activity, Toxicity and Mechanism of Action of Complexes of Sodium Usnate with Lanthanide Ions: Eu(III), Sm(III), Gd(III), Nd(III), La(III) and Tb(III).

Leishmaniases are neglected diseases with limited therapeutic options. Diffuse cutaneous leishmaniasis can occur in Brazil due to Leishmania amazonensis. This study details the antileishmanial activity and cytotoxicity of complexes of sodium usnate (SAU) with lanthanide ions ([LnL3 (H2O)x] (Ln = La(III), Nd(III), Gd(III), Tb(III), Eu(III) and Sm(III); L = SAU). All lanthanide complexes were highly active and more potent than SAU against L. amazonensis promastigotes and intracellular amastigotes (Pro: IC50 < 1.50 µM; Ama: IC50 < 7.52 µM). EuL3·3H2O and NdL3·3H2O were the most selective and effective on intracellular amastigotes, with a selectivity index of approximately 7.0. In silico predictions showed no evidence of mutagenicity, tumorigenicity or irritation for all complexes. Treatment with EuL3·3H2O triggered NO release even at the lowest concentration, indicating NO production as a mechanism of action against the parasite. Incubating promastigotes with the lanthanide complexes, particularly with SmL3·4H2O and GdL3·3H2O, led to a change in the mitochondrial membrane potential, indicating the ability of these complexes to target this essential organelle. The same complexes caused cell death through cell membrane disruption, but their relationship with early or late apoptotic processes remains unclear. Thus, the inclusion of lanthanide ions in SAU improves selectivity with a promising mechanism of action targeting the mitochondria.

Advantages of Using Extremophilic Bacteria for the Biosynthesis of Metallic Nanoparticles and Its Potential for Rare Earth Element Recovery.

The exceptional potential for application that metallic nanoparticles (MeNPs) have shown, has steadily increased their demand in many different scientific and technological areas, including the biomedical and pharmaceutical industry, bioremediation, chemical synthesis, among others. To face the current challenge for transitioning toward more sustainable and ecological production methods, bacterial biosynthesis of MeNPs, especially from extremophilic microorganisms, emerges as a suitable alternative with intrinsic added benefits like improved stability and biocompatibility. Currently, biogenic nanoparticles of different relevant metals have been successfully achieved using different bacterial strains. However, information about biogenic nanoparticles from rare earth elements (REEs) is very scarce, in spite of their great importance and potential. This mini review discusses the current understanding of metallic nanoparticle biosynthesis by extremophilic bacteria, highlighting the relevance of searching for bacterial species that are able to biosynthesize RRE nanoparticles.

Spectroscopic study of the 4fn-15dtransitions of LaPO4doped with Pr3+ or co-doped with Pr3+ and Gd3+ in the vacuum ultra violet region.

The energy off-dtransitions depends on the crystalline field in which the lanthanide ion is inserted. Depending on the experimental setup, these transitions could occur at high energy, so several studies regarding theoretical data have been conducted. Here, we present the experimental determination of the energy of interconfigurational 4fn â†’ 4fn-15d (f-d)transitions from Pr3+ions to the lanthanum orthophosphate LaPO4matrix; we have also determined the bandgap value for this host. The experiments were carried out at the Synchrotron setup of the Brazilian LNLS laboratory. Specifically, we synthesized LaPO4:Pr3+and LaPO4:Pr3+/Gd3+by the hydrothermal method under different pH conditions or by spray pyrolysis. The particles resulting from hydrothermal synthesis had different morphologies and the influence of pH value was showed: the reaction medium was controlled along the process, which changed the surface potential. On the basis of Raman spectroscopy and x-ray diffraction analyses, we found that the crystalline phase was monoclinic monazite for all the samples. We studied the 4f5dlevel and bandgap transitions at high energy by absorption analysis in the VUV range. The experimental results were 7.5 eV (LaPO4bandgap) and 5 eV (4fn→ 4fn-15dtransition of the Pr3+ion), which were close to the theoretical values reported in the literature for this ion and this matrix.

Lanthanide-based ß-Tricalcium Phosphate Upconversion Nanoparticles as an Effective Theranostic Nonviral Vectors for Image-Guided Gene Therapy.

Lanthanide-based beta-tricalcium phosphate (ß-TCP) upconversion nanoparticles are exploited as a non-viral vector for imaging guided-gene therapy by virtue of their unique optical properties and multi-modality imaging ability, high transfection efficiency, high biocompatibility, dispersibility, simplicity of synthesis and surface modification. Ytterbium and thulium-doped ß-TCP nanoparticles (ßTCPYbTm) are synthesized via co-precipitation method, coated with polyethylenimine (PEI) and functionalized with a nuclear-targeting peptide (TAT). Further, in vitro studies revealed that the nanotheranostic carriers are able to transfect cells with the plasmid eGFP at a high efficiency, with approximately 60% of total cells producing the fluorescent green protein. The optimized protocol developed comprises the most efficient ßTCPYbTm/PEI configuration, the amount and the order of assembly of ßTCPYbTm:PEI, TAT, plasmid DNA and the culturing conditions. With having excellent dispersibility and high chemical affinity toward nucleic acid, calcium ions released from ßTCPYbTm:PEI nanoparticles can participate in delivering nucleic acids and other therapeutic molecules, overcoming the nuclear barriers and improving the transfection efficacy. Equally important, the feasibility of the upconversion multifunctional nanovector to serve as an effective contrast agent for imaging modality, capable of converting low-energy light to higher-energy photons via a multi-photons mechanism, endowing greater unique luminescent properties, was successfully demonstrated.

In Vitro Evaluation of the Potential Pharmacological Activity and Molecular Targets of New Benzimidazole-Based Schiff Base Metal Complexes.

Metal-based drugs, including lanthanide complexes, have been extremely effective in clinical treatments against various diseases and have raised major interest in recent decades. Hence, in this work, a series of lanthanum (III) and cerium (III) complexes, including Schiff base ligands derived from (1H-benzimidazol-2-yl)aniline, salicylaldehyde, and 2,4-dihydroxybenzaldehyde were synthesized and characterized using different spectroscopic methods. Besides their cytotoxic activities, they were examined in human U-937 cells, primate kidney non-cancerous COS-7, and six other, different human tumor cell lines: U251, PC-3, K562, HCT-15, MCF-7, and SK-LU-1. In addition, the synthesized compounds were screened for in vitro antiparasitic activity against Leishmania braziliensis, Plasmodium falciparum, and Trypanosoma cruzi. Additionally, antibacterial activities were examined against two Gram-positive strains (S. aureus ATCC® 25923, L. monocytogenes ATCC® 19115) and two Gram-negative strains (E. coli ATCC® 25922, P. aeruginosa ATCC® 27583) using the microdilution method. The lanthanide complexes generally exhibited increased biological activity compared with the free Schiff base ligands. Interactions between the tested compounds and model membranes were examined using differential scanning calorimetry (DSC), and interactions with calf thymus DNA (CT-DNA) were investigated by ultraviolet (UV) absorption. Molecular docking studies were performed using leishmanin (1LML), cruzain (4PI3), P. falciparum alpha-tubulin (GenBank sequence CAA34101 [453 aa]), and S.aureus penicillin-binding protein 2a (PBP2A; 5M18) as the protein receptors. The results lead to the conclusion that the synthesized compounds exhibited a notable effect on model membranes imitating mammalian and bacterial membranes and rolled along DNA strands through groove interactions. Interactions between the compounds and studied receptors depended primarily on ligand structures in the molecular docking study.

Bioinorganic insights of the PQQ-dependent alcohol dehydrogenases.

Among the several alcohol dehydrogenases, PQQ-dependent enzymes are mainly found in the α, ß, and γ-proteobacteria. These proteins are classified into three main groups. Type I ADHs are localized in the periplasm and contain one Ca2+-PQQ moiety, being the methanol dehydrogenase (MDH) the most representative. In recent years, several lanthanide-dependent MDHs have been discovered exploding the understanding of the natural role of lanthanide ions. Type II ADHs are localized in the periplasm and possess one Ca2+-PQQ moiety and one heme c group. Finally, type III ADHs are complexes of two or three subunits localized in the cytoplasmic membrane and possess one Ca2+-PQQ moiety and four heme c groups, and in one of these proteins, an additional [2Fe-2S] cluster has been discovered recently. From the bioinorganic point of view, PQQ-dependent alcohol dehydrogenases have been revived recently mainly due to the discovery of the lanthanide-dependent enzymes. Here, we review the three types of PQQ-dependent ADHs with special focus on their structural features and electron transfer processes. The PQQ-Alcohol dehydrogenases are classified into three main groups. Type I and type II ADHs are located in the periplasm, while type III ADHs are in the cytoplasmic membrane. ADH-I have a Ca-PQQ or a Ln-PQQ, ADH-II a Ca-PQQ and one heme-c and ADH-III a Ca-PQQ and four hemes-c. This review focuses on their structural features and electron transfer processes.

Red-Emitting Hybrid Based on Eu3+-dbm Complex Anchored on Silica Nanoparticles Surface by Carboxylic Acid for Biomarker Application.

Luminescent organic-inorganic hybrids containing lanthanides (Ln3+) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO2) nanospheres decorated with Eu3+ ß-diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO2 surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu3+ to the carboxylate groups and (iv) coordination of dbm- to Eu3+. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu3+-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of -27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu3+ complex provides intense red luminescence, characteristic of Eu3+5D0→7FJ electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging.

Synthesis, Structure Study, First-Principles Investigations and Luminescence Properties of Europium and Terbium Complexes.

The synthesis of 1-benzyl-2-((2-Aminoethyl) amino)-5-oxopyrrolidine-3,4-diyl diacetate (boad), an oxopyrrolidine type ligand; designed to coordinate lanthanides (Eu3+ and Tb3+) to get luminescent material. The target complexes showed good photoluminescence properties, which indicate that this type of compound can be used as sensitizers having luminescence for the green (Tb3+) and red (Eu3+) emission. The obtained results revealed that sensitizer efficiency can be improved by adding ligands like acac (Eu(acac)3, which has also enhanced the luminescence quantum output and period for Eu3+ ions. The ground state geometries were developed by using density functional theory at B3LYP/6-31G** level. The charge transfer analysis and electronic properties were performed. The Europium and Terbium complexes formation with boad ligand was explored based on molecular electrostatic potential, MDC-q charges, and frontier molecular orbitals (FMOs) analysis.

Synthesis, biological evaluation and model membrane studies on metal complexes containing aromatic N,O-chelate ligands.

Novel lanthanide (Ln) compounds [Ln(L)2]Cl.xH2O (Ln = La3+, Ce3+, Sm3+) containing aromatic N,O-chelate ligands [HL1 = 4-amino-2-(1H-benzimidazol-2-yl)phenol; HL2 = 5-amino-2-(1H-benzimidazol-2-yl)phenol] have been synthesized and structurally characterized by elemental analysis, NMR and IR spectroscopy, molar conductance measurements, and mass spectrometry (MS). The spectroscopic data suggested that the benzimidazolyl-phenol ligands act as N,O-chelate ligands through the iminic nitrogen and phenolic oxygen atoms. Elemental analysis indicated that lanthanide compounds were formed in a 1:2 stoichiometry (metal:ligand). In vitro biological evaluation was carried out using these complexes, exhibiting moderate cytotoxicity against six different human tumor cell lines (U251, human glioblastoma; HCT-15, colorectal carcinoma; MCF-7, breast epithelial adenocarcinoma; PC-3, prostate cancer; K562, myelogenous leukemia; SKLU-1, lung carcinoma) and lower toxicity against a non-cancerous cell line (COS-7, primate kidney). In addition, the antibacterial activity of the compounds was assessed against two gram-positive strains (Staphylococcus aureus ATCC 25923, Listeria monocytogenes ATCC 19115) and two gram-negative strains (Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27583) using the microdilution method. The results obtained show that the metal complexes exhibit higher biological activity than the free ligands, confirming a synergistic effect. Further benzimidazolyl-phenol derivatives were explored for the detection of bacteria using fluorescence imaging studies. Interestingly, the fluorescent properties of these compounds make them potential candidates to monitor the morphology of bacteria at different compound concentrations. Hence, the interaction of the ligand and complexes with model membranes mimicking those of bacteria was studied by using differential scanning calorimetry (DSC) and molecular dynamics (MD), showing that both compounds decreased the enthalpy of transition in two model membranes as the concentration of the compounds increased. In addition, the main transition temperature was slightly reduced as a result of these interactions.

Sensing mechanism elucidation of a europium(III) metal-organic framework selective to aniline: A theoretical insight by means of multiconfigurational calculations.

A theoretical procedure, via quantum chemical computations, to elucidate the detection principle of the turn-off luminescence mechanism of an Eu-based Metal-Organic Framework sensor (Eu-MOF) selective to aniline, is accomplished. The energy transfer channels that take place in the Eu-MOF, as well as understanding the luminescence quenching by aniline, were investigated using the well-known and accurate multiconfigurational ab initio methods along with sTD-DFT. Based on multireference calculations, the sensitization pathway from the ligand (antenna) to the lanthanide was assessed in detail, that is, intersystem crossing (ISC) from the S1 to the T1 state of the ligand, with subsequent energy transfer to the 5 D0 state of Eu3+ . Finally, emission from the 5 D0 state to the 7 FJ state is clearly evidenced. Otherwise, the interaction of Eu-MOF with aniline produces a mixture of the electronic states of both systems, where molecular orbitals on aniline now appear in the active space. Consequently, a stabilization of the T1 state of the antenna is observed, blocking the energy transfer to the 5 D0 state of Eu3+ , leading to a non-emissive deactivation. Finally, in this paper, it was demonstrated that the host-guest interactions, which are not taken frequently into account by previous reports, and the employment of high-level theoretical approaches are imperative to raise new concepts that explain the sensing mechanism associated to chemical sensors.

Síntesis, caracterización y evaluación farmacológica de nuevos complejos metálicos derivados de híbridos heteroaromáticos (benzimidazol/oxadiazol) / Synthesis, characterization and pharmacological evaluation of new metal complexes derived from heteroaromatic hybrids (benzimidazole/oxadiazole)

RESUMEN Este documento reporta la síntesis y caracterización detallada de complejos lantánidos La(III), Ce(III), Nd(III) y Sm(III), con ligandos tridentados derivados de híbridos heteroaromáticos. Los ligandos y sus respectivos complejos metálicos fueron caracterizados mediante diferentes técnicas fisicoquímicas, incluyendo análisis elemental y termogravimétrico; espectroscopias UV-Vis, IR, 1H-NMR y 13C-NMR; mediciones de conductancia molar y espectrometría de masas. Los datos espectrales mostraron que el ligando híbrido se comporta como un ligando tridentado NOO a través de los átomos de nitrógeno y oxígeno de los anillos benzimidazol y oxadiazol, así como del átomo de oxígeno del grupo carbonilo. El análisis elemental y térmico mostró que los complejos metálicos obtenidos tienen una estequiometria 1:2 (metal:ligando). Se evaluó la capacidad antioxidante de los compuestos mediante los ensayos DPPH y medidas electroquímicas (voltametría cíclica y voltametría de onda cuadrada). Los resultados mostraron que los complejos metálicos tienen mayor actividad antioxidante que los ligandos libres. Finalmente, la actividad antibacteriana de los ligandos y sus complejos se determinaron mediante pruebas in vitro contra cepas bacterianas Gram positivas y cepas bacterianas Gram negativas utilizando el método de microdilución en caldo. Los complejos metálicos mostraron mayores actividades antimicrobianas que los ligandos precursores contra algunos de los microorganismos.

SUMMARY This paper reports the synthesis and detailed characterization of lanthanide complexes La(III), Ce(III), Nd(III) y Sm(III) with tridentate ligands derived from heteroaromatic hybrids. The ligands and their metal complexes were characterized by different physicochemical techniques, including elemental and thermogravimetric analysis; UV-Vis, IR, 1H-NMR and 13C-NMR spectroscopy; molar conductance measurements; and mass spectrometry. The spectral data showed that the hybrid ligand behaves as a NOO tridentate ligand through the nitrogen and oxygen atoms of the benzimidazole and oxadiazole rings and the oxygen atom of the carbonyl group. Elemental and thermal analyses indicated that the obtained metal complexes were formed in 1:2 stoichiometry (metal-ligand). The antioxidant capacity of these compounds was evaluated by both DPPH assay and electrochemical measurements (cyclic voltammetry and square wave voltammetry). The results showed that the metal complexes have higher antioxidant activity compare to the free ligands. Finally, the antibacterial activities of the ligands and their complexes were determined by in vitro tests against Gram-positive bacterial strains and Gram-negative bacterial strains using the broth microdilution method. The metal complexes showed greater antimicrobial activities than the precursor ligands against some of the microorganisms.

Data of synthesis, characterization and luminescence measurements in 1D lanthanide coordination polymers based on lanthanides.

In this work are presented all the conditions of synthesis explored to obtain a new family of compound with formula [Ln(4-OHBBA)3(H2O)2] (Ln = La, Pr). Powder X ray diffraction was used to identify the different phases obtained in the synthetic study. FT-IR spectroscopy and TG analysis for La and Pr pure phases are also reported. Optical properties of optically active CPs materials, solid state photoluminescence properties of La, Pr, La-(5%Eu) and La-(5%Tb) compounds were explored. We report the absorption, excitation and emission spectrum of the 4'-hydroxi-4-biphenylcarboxylic acid and a comparative description of the radiative (and no-radiative) processes in solid state in Ln-(4-OHBBA) and Ln-BPDC compounds. Finally, a principal component analysis was conducted in order to take in account both signal contributions from the sensor (LCE at 384 nm and the europium emission at 610 nm) and for classifying the type of analytes used to test the sensing response of the materials.

Actinide and Lanthanide Adsorption onto Hierarchically Porous Carbons Beads: A High Surface Affinity for Pu.

Structured carbon adsorbents were prepared by carbonizing macroporous polyacrylonitrile beads whose pores were lined with a mesoporous phenolic resin. After activation, the beads were tested for minor actinide (Np and Am), major actinide (Pu and U) and lanthanide (Gd) adsorption in varying acidic media. The activation of the carbon with ammonium persulfate increased the surface adsorption of the actinides, while decreasing lanthanide adsorption. These beads had a pH region where Pu could be selectively extracted. Pu is one of the longest lived, abundant and most radiotoxic components of spent nuclear fuel and thus, there is an urgent need to increase its security of storage. As carbon has a low neutron absorption cross-section, these beads present an affordable, efficient and safe means for Pu separation from nuclear waste.

Crystal structures of binuclear complexes of gadolinium(III) and dysprosium(III) with oxalate bridges and chelating N,N'-bis-(2-oxido-benz-yl)-N,N'-bis-(pyridin-2-ylmeth-yl)ethyl-enedi-amine (bbpen2-).

The reaction between mononuclear [Ln(bbpen)Cl] [Ln = Gd or Dy; H2bbpen = N,N'-bis-(2-hy-droxy-benz-yl)-N,N'-bis-(pyridin-2-ylmeth-yl)ethyl-enedi-amine, C28H30N4O2] and potassium oxalate monohydrate in water/methanol produced the solvated centrosymmetric isostructural binuclear (µ-oxalato)bis-{[N,N'-bis-(2-oxidobenzyl-κO)-N,N'-bis-(pyridin-2-ylmethyl-κN)ethyl-enedi-amine-κ2 N,N']dilanthanide(III)}-methanol-water (1/4/4) complexes, [Ln 2(C28H28N4O2)2(C2O4)]·4CH3OH·4H2O, with lanthanide(III) = gadolinium(III) (Ln = Gd) and dysprosium(III) (Ln = Dy), in high yields (ca 70%) directly from the reaction mixtures. In both complexes, the lanthanide ion is eight-coordinate and adopts a distorted square-anti-prismatic coordination environment. The triclinic (P ) unit cell contains one dimeric unit together with four water and four methanol mol-ecules; in the final structural model, two of each type of solvating mol-ecule refine well. In each lanthanide(III) dimeric mol-ecule, the medium-strength O⋯H-O hydrogen-bonding pattern involves four oxygen atoms, two of them from the phenolate groups that are 'bridged' by one water and one methanol mol-ecule. These inter-actions seem to contribute to the stabilization of the relatively compact shape of the dimer. Electron densities associated with an additional water and methanol mol-ecule were removed with the SQUEEZE procedure in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. These two new compounds are of inter-est with respect to magnetic properties.

Segmented all-electron basis sets of triple zeta quality for the lanthanides: application to structure calculations of lanthanide monoxides.

Nonrelativistic and relativistic (Douglas-Kroll-Hess, DKH) segmented all-electron Gaussian basis sets of valence triple zeta quality plus polarization functions (TZP) for the lanthanides were developed. As some atomic and molecular properties depend on a good description of the electrons far from the nuclei, these basis sets are augmented with diffuse functions, giving rise to the augmented TZP (ATZP) and ATZP-DKH basis sets. At the DKH level of theory, the B3LYP hybrid functional in conjunction with the TZP-DKH basis set were used to calculate the atomic charges and valence orbital populations of the lanthanide and oxygen atoms, the bond lengths, and the equilibrium dissociation energies of lanthanide monoxides. The DKH-B3LYP/ATZP-DKH polarizability of Yb and the DKH-M06/TZP-DKH first ionization energies of the lanthanides are also reported. Compared with the values obtained with a larger all-electron basis set, and theoretical and experimental data found in the literature, data obtained by our compact basis sets are verified to be accurate and reliable. Unlike effective core potential valence basis sets, our basis sets can also be employed in molecular property calculations that involve the simultaneous treatment of core and valence electrons. Graphical abstract ᅟ.