Dichloro and alkylchloro gallium derivatives of dichalcogenoimidodiphosphinate ligands: isolation of a spirogallium cation

Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-eta2-{R2P(E)NP(E'R'2-E,E'}](X = Cl, R, R'= Ph, E, E'= O (1), S (2), Se (3); R = Ph, R'= OEt, E = O, E'= S (4); R = Me, R'= Ph, E, E'= S (5) and X = Me, E, E'= O (6), S (7), Se (8)) were synthesised by either metathesis reactions between GaCl3 and the potassium salt of the ligand (X = Cl) or by methane eliminations from in situ prepared GaMe2Cl and the protonated ligands LH (X = Me). Redistribution reaction of (3) in either CDCl3 or THF afforded the solvent-free tetracoordinate gallium spirocycle cation [Ga-{eta2-{Ph2P(Se)NP(Se)Ph2-Se,Se'})2]+ (9+). The molecular structures of complexes 2, 4, 5, 7 and 9(+) show non-planar gallacycle rings.     

Rh(I) coordination chemistry of chiral alpha-aminophosphine(eta6-arene)chromium tricarbonyl ligands

The diastereoselective addition of Ph(2)PH to the chiral ortho-substituted eta(6)-benzaldimine complexes (eta(6)-o-X-C(6)H(4)CH=NAr)Cr(CO)(3) (1, X = MeO, Ar = p-C(6)H(4)OMe; 2, X = Cl, Ar = Ph) leads to the formation of the corresponding chiral aminophosphines (alpha-P,N) Ph(2)P-CH(Ar(1))-NHAr(2) (3, Ar(1) = o-C(6)H(4)(OCH(3))[Cr(CO)(3)], Ar(2) = p-C(6)H(4)OCH(3); 4, Ar(1) = o-C(6)H(4)Cl[Cr(CO)(3)], Ar(2) = Ph) in equilibrium with the starting materials. The uncomplexed benzaldimine (o-ClC(6)H(4)CH=NPh), 2', analogously produces an equilibrium amount of the corresponding aminophosphine Ph(2)P-CH(Ar(1))-NHAr(2) (4', Ar(1) = o-C(6)H(4)Cl, Ar(2) = Ph). Depending on the equilibrium constant, the subsequent addition of (1)/(2) equiv of [RhCl(COD)](2) (COD = 1,5-cyclooctadiene) leads to either Ph(2)PH oxidative addition in the case of 3 or to the corresponding [RhCl(COD)(alpha-P,N)] complexes [RhCl(COD)(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)] (5) and [RhCl(COD)(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)] (5') in the cases of the aminophosphines 4 and 4'. The addition of the latter ligands, as racemic mixtures, to (1)/(4) equiv of [Rh(CO)(2)Cl](2) leads to the [RhCl(CO)(alpha-P,N)(2)] complexes [RhCO(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)(2)Cl] (7) or [RhCO(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)(2)Cl] (7') as mixtures of (R(C),S(C))/(S(C),R(C)) and (R(C),R(C))/(S(C),S(C)) diastereomers. The rhodium complexes 5 and 7' have been fully characterized by IR and (31)P NMR spectroscopies and X-ray crystallography. These compounds exhibit intramolecular Rh-Cl.H-N interactions in the solid state and in solution. The stability of the new rhodium complexes has been studied under different CO pressures. Under 1 atm of CO, 5 is converted to an unstable complex [RhCl(CO)(2)(alpha-P,N)], 6, which undergoes ligand redistribution leading to 7 plus an unidentified complex. This reaction is inhibited under higher CO or syngas pressure, as confirmed by the observation of the same catalytic activity in hydroformylation when styrene was added to a catalytic mixture that was either freshly prepared or left standing for 20 h under high CO pressure.     

Determination of aminothiols by liquid chromatography with amperometric detection at a silver electrode: Application to white wines

Liquid chromatography coupled to a silver electrode based flow-through amperometric detector (LC-EC-Ag) was developed for the determination of aminothiols in white wines. The C18 reversed phase LC system operated in the isocratic mode at 0.7 mL min⁻¹ and used an acidic mobile phase composed of formic acid, EDTA, sodium nitrate, sodium hydroxide, and methanol 1% (v/v) at pH 4.5. The working electrode operated at 0.08 V vs Ag/AgCl, 3 M KCl and its manual cleaning was realized once a month by smoothing on a polishing cloth. The analyzed aminothiols were resolved and eluted within 4 min, and all standard curves were linear in the range 2 × 10⁻⁷–2 × 10⁻⁵ M. The analyzed wine samples needed no preparation other than dilution with the mobile phase. The concentration of cysteine (CYS), homocysteine (HCYS), glutathione (GSH) and N-acetylcysteine (NAC) in bottled white wines, determined by the method of standard addition, was found to be in the low μM range (0.2–2 mg L⁻¹) depending on the wine type and its age.     

Optimized Quantitative Method for Determining Isoflavones and Equol in Bovine Digestive Fluids and Feces

Many studies have been conducted on the impact of animal feed on isoflavones and their metabolite concentrations in bovine milk, but few studies have focused on the development and validation of analytical protocols for quantifying these compounds in biological matrices other than milk and plants. The purpose of this study was to develop a method that would enable four isoflavones and equol in cows’ feces and digestive fluids to be quantified simultaneously. The method is based on aglycones released by methanolic ultrasound-assisted extraction, followed by enzymatic hydrolysis and high-performance liquid chromatography tandem–mass spectrometry analysis. The sample preparation was optimized using the Box–Behnken design. The selected extraction conditions were 80°C, 10?min, and 50% methanol for digestive fluids and 70°C, 35?min, and 60% methanol for feces. For hydrolysis, the selected conditions were 37°C, 1?h, and a pH of 6 for both matrices. The analytical method showed a good linear regression model ranging from 5 to 125?ng?mL^?1. Both inter- and intraday accuracy (≤8.5 and ≤12.3%) and precision (≤11.1 and ≤15.2%) were suitable. No matrix effects were found. There was good repeatability and extract stability for at least 4 days of storage at???20 and 6°C. All recoveries were in the acceptable range of 70–120% for both matrices, except for biochanin A in feces, where the value was approximately 43%. This sensitive and reliable method will be useful for monitoring the passage of isoflavones and equol in the digestive system of ruminants.     

First Synthesis of 1,3-Alternate 25,27-Dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 as New Cesium Selective Extractants by Suzuki Cross-coupling Reaction

The synthesis of new 25,27-dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 1a–f in 1,3-alternate conformation by Suzuki cross-coupling reaction is reported. Their conformation was determined using ¹H, ¹³C, 2D NMR and ROESY analysis, and X-ray crystallography. Extraction experiments using a two-phase solvent method involving sodium, potassium or cesium picrate showed good extraction of the cesium cation. The X-ray crystal structures of 1,3-alternate 25,27-dipropoxy-5,17-diphenylcalix[4]arene-crown-6 ether 1a and its cesium picrate complex were established. Solid-state data were used to determine the complexation behavior of these new ligands. The efficiency of calixarenes 1a–f for cesium ion extraction could be ascribed to the rigidity and flatness linkages caused by the aryl groups at the lower rim of the aromatic moieties in the calixarene skeleton. In addition, the introduction of these aromatic moieties in positions 5 and 17 enhanced the solubility of the metal complexes in organic media.     

Active mode locking of continuous-wave doubly and singly resonant optical parametric oscillators

We report on what we believe to be the first active mode locking of near-degenerate, doubly and singly resonant cw-pumped optical parametric oscillators (OPOs). We show experimentally that a steady-state regime of short pulses is reached in a few tens of microseconds under cw pumping. The oscillation buildup dynamics of both OPOs is also explored, evidencing an unusual transient behavior in the mode-locking process.     

N‐(2‐Ethylhexyl)carbazole: A New Fluorophore Highly Suitable as a Monomolecular Liquid Scintillator

The synthesis, photophysical properties, and applications in scintillation counting of N‐(2‐ethylhexyl)carbazole (EHCz) are reported. This molecule displays all of the required characteristics for an efficient liquid scintillator (emission wavelength, scintillation yield), and can be used without any extra fluorophores. Thus, its scintillation properties are discussed, as well as its fast neutron/gamma discrimination. For the latter application, the material is compared with the traditional liquid scintillator BC‐501 A, and other liquid fluorescent molecules classically used as scintillation solvents, such as xylene, pseudocumene (PC), linear alkylbenzenes (LAB), diisopropylnaphthalene (DIN), 1‐methylnaphthalene (1‐MeNapht), and 4‐isopropylbiphenyl (iPrBiph). For the first time, an excimeric form of a molecule has been advantageously used in scintillation counting. A moderate discrimination between fast neutrons and gamma rays was observed in bulk EHCz, with an apparent neutron/gamma discrimination potential half of that of BC‐501 A.     

The Regularity of Optimal Irrigation Patterns

A branched structure is observable in draining and irrigation systems, in electric power supply systems, and in natural objects like blood vessels, the river basins or the trees. Recent approaches of these networks derive their branched structure from an energy functional whose essential feature is to favor wide routes. Given a flow s in a river, a road, a tube or a wire, the transportation cost per unit length is supposed in these models to be proportional to s ^α with 0 < α < 1. The aim of this paper is to prove the regularity of paths (rivers, branches,...) when the irrigated measure is the Lebesgue density on a smooth open set and the irrigating measure is a single source. In that case we prove that all branches of optimal irrigation trees satisfy an elliptic equation and that their curvature is a bounded measure. In consequence all branching points in the network have a tangent cone made of a finite number of segments, and all other points have a tangent. An explicit counterexample disproves these regularity properties for non-Lebesgue irrigated measures.