Hyperbranched polyselenides as glutathione peroxidase mimics

Novel hyperbranched polyselenides with multi-catalytic sites at the branching units have been synthesized which may provide a new approach towards glutathione peroxidase mimics.     

Highly luminescent lanthanide complexes of 1-hydroxy-2-pyridinones

The synthesis, X-ray structure, stability, and photophysical properties of several trivalent lanthanide complexes formed from two differing bis-bidentate ligands incorporating either alkyl or alkyl ether linkages and featuring the 1-hydroxy-2-pyridinone (1,2-HOPO) chelate group in complex with Eu(III), Sm(III), and Gd(III) are reported. The Eu(III) complexes are among some of the best examples, pairing highly efficient emission (Phi tot (Eu) approximately 21.5%) with high stability (pEu approximately 18.6) in aqueous solution, and are excellent candidates for use in biological assays. A comparison of the observed behavior of the complexes with differing backbone linkages shows remarkable similarities, both in stability and photophysical properties. Low temperature photophysical measurements for a Gd(III) complex were also used to gain insight into the electronic structure and were found to agree with corresponding time-dependent density functional theory (TD-DFT) calculations for a model complex. A comparison of the high resolution Eu(III) emission spectra in solution and from single crystals also revealed a more symmetric coordination geometry about the metal ion in solution due to dynamic rotation of the observed solid state structure.     

Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure

A new bis-β-diketone, 3,3'-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln(2)(BTB)(3)(C(2)H(5)OH)(2)(H(2)O)(2)] [Ln = Eu (1), Gd (2)], [Ln(2)(BTB)(3)(DME)(2)] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu(2)(BTB)(3)(L)(2)] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1-7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3-7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu(3+) complexes are determined and described.     

Highly syndiospecific polymerization of styrene catalyzed by allyl lanthanide complexes

Allylic complexes of lanthanides bearing a fluorenyl-based ligand are active single-component catalysts for the polymerization of styrene, giving highly syndiotactic polymers (rrrr > 99%) with low to high molecular weight (Mn = 8000-135 000) and narrow polydispersities (Mw/Mn = 1.25-2.1).     

Thermodynamic properties of samarium and gadolinium polyselenides

The thermodynamic characteristics (Δ_rH₂₉₈, Δ_rS^°₂₉₈) for the stepwise dissociation processes in the systems SmSe_1.9–SmSe_1.5 and GdSe_1.875–GdSe_1.5 were calculated from p_Se–T–x dependences obtained by the static method with quartz membrane-gauge manometers. Solid phase compositions in the systems studied submit to the same dependence (Ln_nSe_2n−1) which was found by us earlier for the other similar systems. Estimations of entropies and heat capacities of the intermediate polyselenides were carried out by the additive rule with use as reference values of LnSe_1.5 thermodynamic characteristics. In this regard, data obtained earlier for the phases GdSe_x (x = 1.85, 1.875) were reprocessed. From the presented information the existence of individual linear phases of polyselenides was proved and a set of standard thermodynamic functions (Δ_fH₂₉₈, S^°₂₉₈, Δ_fG^°₂₉₈) were determined for each polyselenide.     

Highly emissive,nine-coordinate enantiopure lanthanide complexes incorporating tetraazatriphenylenes as probes for DNA

The interaction of q = 0 delta- and lambda-Tb and Eu complexes with poly(dAdT), poly(dGdC) and calf-thymus DNA has been examined by absorption, emission and chiroptical spectroscopy and is sensitive to complex helicity, base-pair type and the nature of the lanthanide excited state.     

Reduction of biselenites into polyselenides in interlayer space of layered double hydroxides

A selenous acid (H₂SeO₃) precursor was intercalated as biselenite (HSeO₃⁻) ions into the interlayer gallery of carbonated magnesium aluminum layered double hydroxide (MgAl-LDH) in aqueous solution. Reduction reaction of selenous ions by aqueous hydrazine solution produced polyselenide intercalated LDHs which were consecutively exchanged with iodide through redox reaction under iodine vapor. The polyselenide containing LDHs adsorbed iodine vapor spontaneously and triiodide was incorporated in the interlayer space followed by formation of selenium polycrystalline phase. Two dimensional framework of MgAl-LDH is strong enough to resist against the reducing power of hydrazine as well as oxidation condition of iodine. The SEM data demonstrated that the shapes of LDH polycrystalline have little changed after the above redox reactions. The polyselenide and iodide LDH products were analyzed by XRD, Infrared and Raman spectra which strongly suggested the horizontal arrangement of polyselenide and triiodide in gallery space of LDHs.     

Highly atom efficient guanylation of both aromatic and secondary amines catalyzed by simple lanthanide amides

It is demonstrated that the cyclopentadienyl-free simple lanthanide amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln = La, Sm, Eu, Y, Yb) and Ln[N(SiMe(3))(2)]3 (Ln = Y, Yb) are highly efficient catalysts for the guanylation of both aromatic and secondary amines with a high activity under mild conditions. It is found that these catalysts are compatible with a wide range of solvents and substrates.     

Highly luminescent, visible-emitting lanthanide macrocyclic chelates stable in water and derived from the cyclen framework

Two new tetraazamacrocyclic ligands are designed with the aim of sensitizing the luminescence of Tb(III) and Eu(III) ions in water: L5 [1,4,7,10-tetrakis[N-(phenacyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane] and L6 [1,4,7,10-tetrakis[N-(4-phenylphenacyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane]. These ligands react with lanthanide trifluoromethanesulfonates to yield stable 1:1 complexes in water (log K = 12.89 +/- 0.15 for EuL5). X-ray diffraction on [Tb(L5)(H(2)O)](CF(3)SO(3))(3) (P1 macro, a = 13.308(3) A, b = 14.338(3) A, c = 16.130(3) A, alpha = 101.37(3) degrees, beta = 96.16(3) degrees, gamma = 98.60(3) degrees ) shows the Tb(III) ion lying on a C(4) axis and being 9-coordinate, with one water molecule bound in its inner coordination sphere. The absolute quantum yields are determined in aerated water for the complexes formed with ions used in fluoroimmunoassays (Ln = Sm, Eu, Tb, and Dy). Large values are found for [Tb(H(2)O)(L5)](3+) and [Eu(H(2)O)(L6)](3+), in line with the molecular design of the receptors: 23.1% and 24.7%, respectively. The intense luminescence of these ions results from efficient intersystem crossing and L --> Ln energy transfer processes, as well as from a suitable shielding of the emitting ions from radiationless deactivation.     

Nanoparticle-encapsulated vis- and NIR-emissive fluorophores with different fluorescence decay kinetics for lifetime multiplexing

Bioanalytical, clinical, and security applications increasingly require simple, efficient, and versatile strategies to measure an ever increasing number of analytes or events in parallel in a broad variety of detection formats as well as in conjunction with chromatographic separation techniques or flow cytometry. An attractive alternative to common optical multiplexing and encoding methods utilizing spectral multiplexing/color encoding and intensity encoding is lifetime multiplexing, which relies on the discrimination between different fluorescent reporters based on their fluorescence decay kinetics. Here, we propose a platform of surface-functionalizable polymeric nanoparticles stained with fluorophores differing in their fluorescence lifetimes as a new multiplexing and encoding approach. Proof-of-concept measurements with different sets of lifetime-encoded polystyrene nanoparticles are presented, obtained via staining of preformed particles with visible (vis)- and near-infrared (NIR)-emissive organic dyes, which display very similar absorption and emission spectra to enable excitation and detection at the same wavelengths, yet sufficiently different fluorescence decay kinetics in suspension, thereby minimizing instrumentation costs. Data analysis was performed with a linear combination approach in the lifetime domain. Our results and first cell experiments with these reporter sets underline the suitability of our multiplexing strategy for the discrimination between and the quantification of different labels. This simple and versatile concept can be extended to all types of fluorophores, thereby expanding the accessible time scale, and can be used, e.g., for the design of labels and targeted probes for fluorescence assays and molecular imaging, cellular imaging studies, and barcoding applications, also in conjunction with spectral and intensity encoding.

Mechanisms of sensitization of lanthanide(III)-based luminescence in transition metal/lanthanide and anthracene/lanthanide dyads

Four sets of dyads are discussed, in all of which near-infrared emitting lanthanide(III) ions such as Nd(III), Er(III) or Yb(III) are energy-acceptors which provide sensitized luminescence following energy-transfer from an antenna group. In three sets of dyads the antenna (energy-donor) group is a luminescent transition metal fragment; in the fourth the antenna is an anthracene group. A combination of photophysical studies and calculations has been used to understand the mechanisms by which energy-transfer to the lanthanide(III) ion occurs. Although definitive answers are not possible in every case due to the presence of several possible energy-transfer pathways, the relative contributions of Förster-type, Dexter-type and redox-mediated energy-transfer pathways have been analysed. Interesting results include (i) the demonstration of pure Dexter energy-transfer over 20 Å in a Ru(II)/Nd(III) dyad, and (ii) the demonstration of a redox-based mechanism for energy-transfer in anthracene/Ln(III) dyads in which the first step is photoinduced electron-transfer from the excited anthracene chromophore to a diimine ligand on the lanthanide(III) to generate a charge-separated state.     

Complexation of lanthanide nitrates

Summary The change of the stability constantsK ⁰ ₁ of the lanthanide nitrato complexes in the lanthanide series is presented and discussed from the viewpoint of the interaction between the first and second hydration sheath of lanthanide ions.

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Komplexierung bei Lanthaniden-Nitraten

Zusammenfassung Es wird der Verlauf der StabilitätskonstantenK ⁰ ₁ von Nitrato-Komplexen in der Lanthanidenreihe vorgestellt und auf Basis von Wechselwirkungen zwischen der ersten und zweiten Hydrat-Schicht der Lanthaniden-Ionen diskutiert.

     

Photoluminescent layered lanthanide silicates

The hydrothermal synthesis and structural characterization of layered lanthanide silicates, K(3)[M(1-a)Ln(a)Si(3)O(8)(OH)(2)] (M = Y(3+), Tb(3+); Ln = Eu(3+), Er(3+), Tb(3+), and Gd(3+)), named AV-22 materials, are reported. The structure of these solids was elucidated by single-crystal (180 K) and powder X-ray diffraction and further characterized by chemical analysis, thermogravimetry, scanning electron microscopy, (29)Si MAS NMR, and photoluminescence spectroscopy. The Er-AV-22 material is a room-temperature infrared phosphor, while Tb- and Eu-AV-22 are visible emitters with output efficiencies comparable to standards used in commercial lamps. The structure of these materials allows the inclusion of a second (or even a third) type of Ln(3+) ion in the framework and, therefore, the fine-tuning of their photoluminescent properties. For the mixed Tb(3+)/Eu(3+) materials, evidence has been found of the inclusion of Eu(3+) ions in the interlayer space by replacing K+ ions, further allowing the activation of Tb(3+)-to-Eu(3+) energy transfer mechanisms. The occurrence probability of such mechanisms ranges from 0.62 (a = 0.05) to 1.20 ms(-1) (a = 0.1) with a high energy transfer efficiency (0.73 and 0.84, respectively).     

Triboluminescence of lanthanide acetylacetonates

Triboluminescence of Ln(acac)₃·H₂O (Ln = Tb, Eu, Pr, Ce, Gd) was found. The UV radiation was detected for the first time as narrow bands caused by the emission of the adsorbed N₂* molecules (transitions ³∏_u → ³∏_g) in the study of triboluminescence of lanthanide compounds. The emission of Ln³⁺* (ionic triboluminescence) was observed only for Tb³⁺* (λ_max/nm: 490 (⁵D₄-⁷F₆), 545 (⁵D₄-⁷F₅), 580 (⁵D₄-⁷F₄)) and Eu³⁺* (λ?max/nm: 613, 614 (⁵D₂-⁷F₃)). The generation of N₂* occurs due to the energy of electric fields appeared upon the destruction of crystalline samples of Ln(acac)₃·H₂O. The Tb³⁺* and Eu³⁺* ions are formed due to the energy transfer from the triplet level of the ligand (acacT₁), which is excited by the light emitted from the N₂* molecule.     

The lanthanide contraction revisited

A complete, isostructural series of complexes with La-Lu (except Pm) with the ligand TREN-1,2-HOIQO has been synthesized and structurally characterized by means of single-crystal X-ray analysis. All complexes are 1D-polymeric species in the solid state, with the lanthanide being in an eight-coordinate, distorted trigonal-dodecahedral environment with a donor set of eight unique oxygen atoms. This series constitutes the first complete set of isostructural complexes from La-Lu (without Pm) with a ligand of denticity greater than two. The geometric arrangement of the chelating moieties slightly deviates across the lanthanide series, as analyzed by a shape parameter metric based on the comparison of the dihedral angles along all edges of the coordination polyhedron. The apparent lanthanide contraction in the individual Ln-O bond lengths deviates considerably from the expected quadratic decrease that was found previously in a number of complexes with ligands of low denticity. The sum of all bond lengths around the trivalent metal cation, however, is more regular, showing an almost ideal quadratic behavior across the entire series. The quadratic nature of the lanthanide contraction is derived theoretically from Slater's model for the calculation of ionic radii. In addition, the sum of all distances along the edges of the coordination polyhedron show exactly the same quadratic dependence as the Ln-X bond lengths. The universal validity of this coordination sphere contraction, concomitant with the quadratic decrease in Ln-X bond lengths, was confirmed by reexamination of four other, previously published series of lanthanide complexes. Owing to the importance of multidentate ligands for the chelation of rare-earth metals, this result provides a significant advance for the prediction and rationalization of the geometric features of the corresponding lanthanide complexes, with great potential impact for all aspects of lanthanide coordination.     

Hydrates of lanthanide triiodides

Hydrates of the lanthanide triiodides have been synthetized by evaporation of water from aqueous LnI₃ solutions. The highest hydrated states are nonahydrates of the iodides of the larger lanthanides, (La-Dy) and octahydrates of the iodides of the smaller ones, (Tb-Lu) whereas Tb and Dy form nonahydrates as well as octahydrates. Dehydration of the nona- or octahydrates at 10⁻¹ torr and room temperature results in the formation of hexahydrates of all rare earth iodides. Heating of the hexahydrates of the larger lanthanides La, Ce, Pr and Nd at 50°C (10⁻¹ torr) leads to the formation of trihydrates and anhydrous salts. With the other hexahydrates decomposition was observed.     

Monodisperse lanthanide oxysulfide nanocrystals

Monodisperse lanthanide oxysulfide nanoplates and short nanorods were synthesized by the thermal decomposition of molecular precursors in the presence of oxygen. The nanoplates have uniform thicknesses and further self-organize to nanowires up to micron scale. The Eu2O2S and Eu3+-doped Gd2O2S nanocrystals both show unusual fluorescence properties obviously differing from the bulk powder phosphors, which are related to the surface-modification effects.     

Synthesis of lanthanide carbonates

The normal carbonates of La³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Dy³⁺ and Ho³⁺ have been synthesized by the reaction of an aqueous suspension of the lanthanide oxide, M₂O₃, with CO₂ under supercritical conditions. The effect of temperature, between 25 and 50 °C, and pressure, from 68 to 240 atm, on the extent of conversion of the oxide to the carbonate has been investigated. Yields of 95% or better of the normal carbonates were obtained at a pressure of 100 atm after the reaction was carried out for 1 h. The higher the concentration of CO₂ dissolved in the aqueous phase, the higher the yield. The oxides of Pr³⁺, Tb³⁺, Er³⁺ and Yb³⁺, as well as ZrO₂ and CeO₂, either did not react at all or gave very low yields of carbonates under the experimental conditions that were employed.