Influence of the Lanthanide Ion and Solution Conditions on Formation of Lanthanide Wells–Dawson Polyoxotungstates

Lanthanide complexes of polyoxometalates, including the α₂-P₂W₁₇O₆₁ ¹⁰⁻ ligand, have been pioneered by Michael T. Pope, to whom this paper is dedicated. Examination of the solid-state and solution behavior of lanthanide complexes of the α₂-P₂W₁₇O₆₁ ¹⁰⁻ ligand are reported here to identify trends that will facilitate rational synthesis of hybrid organic lanthanide polyoxometalate complexes. Therefore, combining our data with that obtained by Pope and others a number of trends come into view. It is clear that there are two structural types for the 1:1 or 2:2 [Ln(H₂O)_X(α₂-P₂W₁₇O₆₁)]₂ ¹⁴⁻ species. The early lanthanides show a “cap to cap” structure that allows the Ln ion to be 9 coordinate and accommodates the longer bond lengths. The mid-late lanthanides show a “cap to belt” structure that allows the lanthanides to be 8 coordinate; this structural type is appropriate for the shorter bond lengths of the later lanthanides. The 1:1⇌1:2 equilibrium, that was observed by Pope for the Ce(III) analog is prevalent for the early- mid lanthanides. This equilibrium is slightly dependent on pH; however, cations have a major influence on this equilibrium. Larger, poorly hydrated cations appear to favor the 1:2 species for the early to mid lanthanides. Cations do not appear to influence the equilibrium for the later lanthanides; for all counterions, the 1:1 species was stable with no trace of the 1:2 species. Stability constants, K1 and K2, for the early to mid lanthanides were measured in this study by a competitive method and compared well with other published stability constant determinations. We suggest that the stability constants are not only dependent on the strength of interaction of the Ln with the α₂-P₂W₁₇O₆₁ ¹⁰⁻ ligand, but are also significantly influenced by the medium. The medium may bias the equilibria of the early-mid lanthanides and later lanthanides. The log K₁/log K₂ ratios are very close, suggesting that it is difficult to separate the 1:1 and 1:2 Ln: α₂-P₂W₁₇O₆₁ ¹⁰⁻ species.Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.This paper is dedicated to Professor Michael T. Pope in honor of his substantial and sustained contributions to polyoxometalate chemistry and his inspiration to scientists working in the field.     

Direct 2-Arylation of Thiophene Using Low Loading of a Phosphine-Free Palladium Catalyst

The direct coupling of aryl halides with thiophene would be a considerable advantage for sustainable development because of only HBr associated with a base as by-product is formed and the number of steps to prepare these compounds is less than in more classical coupling reactions. We observed that through the use of only 0.2 mol% Pd(OAc)₂ as the catalyst, a range of aryl bromides undergoes coupling via a C-H bond activation/functionalization reaction with thiophene to give 2-arylated thiophenes in good yields. In most cases, only traces of polyarylated thiophenes were detected when a large excess of thiophene was employed. This air-stable catalyst can be used with a wide variety of aryl bromides.      

Metal‐Triflate‐Catalyzed Synthesis of Polycyclic Tertiary Alcohols by Cyclization of γ‐Allenic Ketones

It has been established that bismuth(III) triflate catalyzes the cyclization of γ‐allenic ketones under mild reaction conditions. This reaction allows the selective formation of polycyclic tertiary alcohols from cyclic ketone derivatives. The resulting dienols can engage in stereoselective cycloadditions to efficiently afford complex polycyclic systems.     

Circular polarization of the (1s2p)2 → (1s2)0 line emitted by 205Tl79+ ions after collisional excitation by an unpolarized electron beam

The circular polarization of the (1s2p)_J=2 → (1s²)_J=0 line emitted by the helium-like ion ²⁰⁵Tl⁷⁹⁺ following impact excitation by a nonpolarized electron beam is theoretically studied. The probability for the hyperfine induced E1 transition (1s2p)₂F=3/2→1s² has been determined from the first order perturbation theory. Various collision strengths for excitation of thallium ions to the (1s2p)₂M_J=0, 1 and 2 magnetic sublevels have been used. It is found that the interference between M2 and E1 radiation occurring in the line can give rise to a significant degree of circular polarization. This revised version was published online in August 2006 with corrections to the Cover Date.     

Catalyse par transfert de phase solide-liquide sans solvant : application a la reaction de michael

Solid-liquid phase transfer catalysis without added organic solvent efficiently promotes MICHAEL reactions. The method is applied here to the addition of acetylacetone, methylacetoacetate and fluorene anions on hindered acceptors.     

Solubility effects of multicomponent liquid crystal blends towards poly (n-butyl-acrylate)

Blends composed of isotropic linear poly (n-butylacrylate) of molecular weight M _w?=?112,000 g mol^?1 and the commercial four-component nematic low molecular weight liquid crystal (LC) mixture E7 exhibit a strong shift of the single nematic–isotropic transition temperature T _NI compared to that of the pure LCs, which was evidenced by using two complementary experimental techniques: differential scanning calorimetry (DSC) and high-performance liquid chromatography. The first one provides direct information about phase behaviour and variation of T _NI of the polymer/LC blends, whereas the second one consists of analysing qualitatively and quantitatively the composition of millimetre-sized segregated LC domains in the two-phase region of the phase diagram.

In order to understand the origin of the unusual phase behaviour, several LC blends were prepared by modifying the concentration of the four single LC components that are present in the eutectic E7 mixture, following the results from the previous chromatographic analysis. These model blends were investigated by DSC measurements, showing that the variation, particularly of the terphenyl LC compound concentration, plays a determining role for the phase behaviour of the LC mixture and the shift of T _NI.     

Contribution of oenocytes and pheromones to courtship behaviour in Drosophila

Background  

In Drosophila, cuticular sex pheromones are long-chain unsaturated hydrocarbons synthesized from fatty acid precursors in epidermal cells called oenocytes. The species D. melanogaster shows sex pheromone dimorphism, with high levels of monoenes in males, and of dienes in females. Some biosynthesis enzymes are expressed both in fat body and oenocytes, rendering it difficult to estimate the exact role of oenocytes and of the transport of fatty acids from fat body to oenocytes in pheromone elaboration. To address this question, we RNAi silenced two main genes of the biosynthesis pathway, desat1 and desatF, in the oenocytes of D. melanogaster, without modifying their fat body expression.     

A Laccase/Chitosan‐Lambda‐Carrageenan Based Voltammetric Biosensor for Phenolic Compound Detection

In this contribution, a new concept of voltammetric catechol biosensor, based on the encapsulation of laccase (LAC) in a chitosan+lambda‐carrageenan (CHIT+CAR) polyelectrolyte complex (PEC) employing a simple coacervation process is presented. Chitosan (CHIT) was prepared from α‐chitin extracted from shrimp shells and lambda‐carrageenan (CAR) was extracted from red algae, both polysaccharides and PEC being characterized using FTIR spectrometry and electrochemistry. Cyclic voltammetry was utilized to determine the analytical features of the laccase (LAC) biosensor for catechol detection. The linear range was from 10^?20 M to 10^?14 M with a sensitivity of 1.55 mA/p[catechol] and a limit of detection of 3×10^?21 M.The laccase biosensor exhibits good repeatability (RSD 2.38 %) and stability (four weeks). The developed biosensor was tested by applying it to the evaluation of the total polyphenolic content in natural oil samples.