Optical gain by upconversion in Tm–Yb oxyfluoride glass ceramic

Evidence of positive optical gain is observed in Tm³⁺–Yb³⁺-codoped oxyfluoride glass ceramic in an upconversion pump and probe experiment. The ¹G₄ level of the Tm³⁺ ions is populated by an upconversion mechanism under excitation of the Yb³⁺ ions at 975 nm with a high-power pulsed laser and give rise to an intense emission from the ¹G₄ to the ³F₄ levels. The ¹G₄→³F₄ electronic transition is stimulated with a low signal at 650 nm as a probe.     

Validated assay for studying activity profiles of human liver UGTs after drug exposure: inhibition and induction studies

UDP-glucuronsyltransferases (UGTs) are a family of conjugating enzymes that participate in the metabolism of many drugs. The study of potential drug–drug interactions involving UGTs has been largely hindered by the limited availability of selective functional assays for individual UGT enzymes. We propose a sensitive and reproducible procedure for the activity measurements of four major human hepatic UGT forms. The assays are based on analysis and quantification by high-performance liquid chromatography–tandem mass spectrometry of glucuronides formed from selective probe substrates, namely, β-estradiol (UGT1A1, 3-glucuronide), 1-naphthol (UGT1A6), propofol (UGT1A9), and naloxone (UGT2B7). The analytical methods developed in the present study have been validated under good laboratory practice compliance following FDA recommendations. The assays can be easily applied to both phenotyping UGT reactions in liver-derived cellular and subcellular systems, and drug–drug interaction in vitro studies. Chemical inhibition of UGTs was tested in human liver microsomes at substrate concentrations lower than the corresponding K _M values. Under these conditions, selective inhibition of UGT2B7 by fluconazole and low amitriptyline concentrations were observed, whereas diclofenac and quinidine were shown as non-enzyme-selective inhibitors of UGTs. Induction of UGTs was studied in primary human hepatocytes and HepG2 cells cultured in 96-well plates. Aryl hydrocarbon receptor ligands (except indirubin in hepatocytes) increased the UGT1A1 activity in both cell models. The highest effects were observed in HepG2 cells exposed to indirubin (21-fold over the control) and omeprazole or β-naphthoflavone (about sixfold). Although variable effects were observed in other UGT enzymes, the degree of induction was generally lower than that for UGT1A1.     

Ruthenium amino carboxylate complexes as asymmetric hydrogen transfer catalysts

The synthesis and characterization of optically active amino carboxylate complexes of formula [(η(6)-arene)Ru(Aa)Cl] (arene = C(6)H(6), C(6)Me(6), Aa = amino carboxylate) as well as those of the related trimers [{(η(6)-arene)Ru(Aa)}(3)][BF(4)](3) are reported. Trimerization takes place with chiral self-recognition: only diastereomers equally configured at the metal, R(Ru)R(Ru)R(Ru) or S(Ru)S(Ru)S(Ru), are detected. The crystal structures of the complexes [(η(6)-C(6)H(6))Ru(Pip)Cl] and [{(η(6)-C(6)Me(6))Ru(Pro)}(3)][BF(4)](3) have been determined by X-ray diffraction methods. Both types of complexes catalyse the hydrogen transfer reaction from 2-propanol to ketones with moderate enantioselectivity (up to 68% ee). The enantiodifferentiation achieved can be accounted for by assuming that Noyori's bifunctional mechanism is operating.     

Isolation, X-ray structure and properties of an unusual pentacarbonyl(2,2′-pyridyl-quinoxaline) tungsten complex

The first example of a monodentate complexation of 2-(2′-pyridyl)quinoxaline (pq) to a metal centre through N₄ is reported. Photochemical exchange of the THF ligand in W(CO)₅THF by pq yields W(CO)₅(N₄-pq) (1), where the potentially bidentate pq ligand coordinates in an unusual monodentate fashion. Complex 1 is isolated as orange crystals and fully characterized on the basis of NMR, IR, UV-Vis and emission spectroscopy. The structure of 1 was determined by X-ray analysis. W(CO)₅(N₄-pq) (1) crystallizes in space group P2_1/n, monoclinic crystal system with α = 7.0237(5) Å, b = 10.4618(8) Å, c = 23.7768(18) Å, Z = 4 and V = 1731.9(2) Å³. Complex 1 exhibits intramolecular CH?N and intermolecular CH?O hydrogen bonds between the CH groups and nitrogen atoms of quinoxaline and CH groups and oxygen atoms of carbonyls, respectively, resulting in a supramolecular architecture in solid state. The preference to N₄ as coordination site is discussed in terms of electronic interactions. Solutions of 1 emits dually at 77 K while they are moderately instable at room temperature, as 1 undergoes chelation via a first-order kinetic process to form W(CO)₄pq (2). The determined reaction rate of 1 in toluene is 2.3 × 10⁻⁵ s⁻¹ (at 298 K) and is compared with literature values for other W(CO)₅L (L:diimine) complexes.     

Preparation and application of silicalite-1 micromembranes on laser-perforated stainless steel sheets

Silicalite-1 micromembranes of approximately 80 μm in diameter have been prepared by synthesizing the zeolite material inside a network of perforations created by using a Nd–YAG laser on 75 μm thick stainless steel sheets. Several strategies have been introduced here to reduce the thickness of the micromembranes synthesized; among these the most successful involved using a polyamide filling to reduce the volume of the microperforations accessible to the synthesis solution. The density of microperforations could be tailored to prepare arrays of micromembranes of different overall porosity (1.8, 3.7, 6.6 and 7.7%). The micromembranes performed well in the propane/N₂ separation, showing a maximum propane/N₂ separation factor of 46, at a propane permeance of about 5 × 10⁻⁶ mol/(m² s Pa).     

The C form of n‐hexa­decanoic acid

In the crystal structure of the title compound, C₁₆H₃₂O₂, the mol­ecules are arranged into dimers through O—H⋯O hydrogen bonds. These dimers are packed in bilayers with terminal methyl groups at both external faces, and these layers are parallel to the crystallographic (100) plane. All C—C bonds of the alkyl chain show an anti­periplanar (trans) conformation, with slight deviations from the ideal value in the C—C bonds close to the inter­molecular hydrogen bonds. The similarity between the carb­oxyl C—O bond distances is consistent with the existence of cis–trans tautomerism.     

C?NH2 Bond Formation Mediated by Iridium Complexes

In the presence of phosphanes (PR₃), the amido‐bridged trinuclear complex [{Ir(μ‐NH₂)(tfbb)}₃] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2‐η²‐4‐κ‐C₁₂H₈F₄N)(PR₃)₃], which are the products of the C N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e⁻ complex [Ir(Cl)(tfbb)(PMePh₂)₂] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH₂ moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule.     

Hydride‐Rhodium(III)‐N‐Heterocyclic Carbene Catalysts for Vinyl‐Selective H/D Exchange: A Structure–Activity Study

A series of neutral and cationic Rh^III‐hydride and Rh^III‐ethyl complexes bearing a NHC ligand has been synthesized and evaluated as catalyst precursors for H/D exchange of styrene using CD₃OD as a deuterium source. Various ligands have been examined in order to understand how the stereoelectronic properties can modulate the catalytic activity. Most of these complexes proved to be very active and selective in the vinylic H/D exchange, without deuteration at the aromatic positions, displaying very high selectivity toward the β‐positions. In particular, the cationic complex [RhClH(CH₃CN)₃(IPr)]CF₃SO₃ showed excellent catalytic activity, reaching the maximum attainable degree of β‐vinylic deuteration in only 20 min. By modulation of the catalyst structure, we obtained improved α/β selectivity. Thus, the catalyst [RhClH(κ²‐O,N‐C₉H₆NO)(SIPr)], bearing an 8‐quinolinolate ligand and a bulky and strongly electron‐donating SIPr as the NHC, showed total selectivity for the β‐vinylic positions. This systematic study has shown that increased electron density and steric demand at the metal center can improve both the catalytic activity and selectivity. Complexes bearing ligands with very high steric hindrance, however, proved to be inactive.