Redox Non‐Innocence of Nitrosobenzene at Nickel

Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox‐active nitric oxide derivative. Capture of nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [ⁱPr₂NN_F6]Ni results in reduction of the PhNO ligand to a (PhNO)^./? species coordinated to a square planar Ni^II center in [ⁱPr₂NN_F6]Ni(η²‐ONPh). Ligand centered reduction leads to the (PhNO)^2? moiety bound to Ni^II supported by XAS studies. Systematic investigation of structure–reactivity patterns of (PhNO)^./? and (PhNO)^2? ligands reveals parallels with superoxo (O₂)^./? and peroxo (O₂)^2? ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.     

Quantum yields of the mercury photosensitized cis-trans isomerization of 1,3-pentadiene

The quantum yields of thecis trans andtrans cis Hg 6(³P₁) photosensitized isomerizations of 1,3-pentadiene at 100 Torr and 22°C are 0.54±0.02 and 0.42±0.02, respectively. The steady state ratio ([trans]/[cis])_ss is 1.27±0.05 which is almost identical with the ratio of the quantum yields, (ct)/(tc)=1.29±0.10. Thecistrans isomerization is suggested as a useful actinometer for mercury sensitized reactions.

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Hg 6(³P₁) 1,3- 100 22°C 0,54±0,02 0,42±0,02, . ([]/[]) 1,27±0,05, ( )/( )=1,29±0,10. , .

     

Fast 3D shape screening of large chemical databases through alignment-recycling

Background  

Large chemical databases require fast, efficient, and simple ways of looking for similar structures. Although such tasks are now fairly well resolved for graph-based similarity queries, they remain an issue for 3D approaches, particularly for those based on 3D shape overlays. Inspired by a recent technique developed to compare molecular shapes, we designed a hybrid methodology, alignment-recycling, that enables efficient retrieval and alignment of structures with similar 3D shapes.     

Control of the evolution of iron peroxide intermediate in superoxide reductase from Desulfoarculus baarsii. Involvement of lysine 48 in protonation

Superoxide reductase is a nonheme iron metalloenzyme that detoxifies superoxide anion radicals O(2)(?-) in some microorganisms. Its catalytic mechanism was previously proposed to involve a single ferric iron (hydro)peroxo intermediate, which is protonated to form the reaction product H(2)O(2). Here, we show by pulse radiolysis that the mutation of the well-conserved lysine 48 into isoleucine in the SOR from Desulfoarculus baarsii dramatically affects its reaction with O(2)(?-). Although the first reaction intermediate and its decay are not affected by the mutation, H(2)O(2) is no longer the reaction product. In addition, in contrast to the wild-type SOR, the lysine mutant catalyzes a two-electron oxidation of an olefin into epoxide in the presence of H(2)O(2), suggesting the formation of iron-oxo intermediate species in this mutant. In agreement with the recent X-ray structures of the peroxide intermediates trapped in a SOR crystal, these data support the involvement of lysine 48 in the specific protonation of the proximal oxygen of the peroxide intermediate to generate H(2)O(2), thus avoiding formation of iron-oxo species, as is observed in cytochrome P450. In addition, we proposed that the first reaction intermediate observed by pulse radiolysis is a ferrous-iron superoxo species, in agreement with TD-DFT calculations of the absorption spectrum of this intermediate. A new reaction scheme for the catalytical mechanism of SOR with O(2)(?-) is presented in which ferrous iron-superoxo and ferric hydroperoxide species are reaction intermediates, and the lysine 48 plays a key role in the control of the evolution of iron peroxide intermediate to form H(2)O(2).     

Comparison of solvent mixtures for pressurized solvent extraction of soil fatty acid biomarkers

The extraction and transesterification of soil lipids into fatty acid methyl esters (FAMEs) is a useful technique for studying soil microbial communities. The objective of this study was to find the best solvent mixture to extract soil lipids with a pressurized solvent extractor system. Four solvent mixtures were selected for testing: chloroform:methanol:phosphate buffer (1:2:0.8, v/v/v), chloroform:methanol (1:2, v/v), hexane:2-propanol (3:2, v/v) and acetone. Soils were from agricultural fields and had a wide range of clay, organic matter and microbial biomass contents. Total lipid fatty acid methyl esters (TL-FAMEs) were the extractable soil lipids identified and quantified with gas chromatography and flame ionization detection. Concentrations of TL-FAMEs ranged from 57.3 to 542.2 n mole g⁻¹ soil (dry weight basis). The highest concentrations of TL-FAMEs were extracted with chloroform:methanol:buffer or chloroform:methanol mixtures than with the hexane:2-propanol or acetone solvents. The concentrations of TL-FAMEs in chemical groups, including saturated, branched, mono- and poly-unsaturated and hydroxy fatty acids were assessed, and biological groups (soil bacteria, mycorrhizal fungi, saprophytic fungi and higher plants) was distinguished. The extraction efficiency for the chemical and biological groups followed the general trend of: chloroform:methanol:buffer ≥ chloroform:methanol > hexane:2-propanol = acetone. Discriminant analysis revealed differences in TL-FAME profiles based on the solvent mixture and the soil type. Although solvent mixtures containing chloroform and methanol were the most efficient for extracting lipids from the agricultural soils in this study, soil properties and the lipid groups to be studied should be considered when selecting a solvent mixture. According to our knowledge, this is the first report of soil lipid extraction with hexane:2-propanol or acetone in a pressurized solvent extraction system.     

Influence of the Metal Ion on the Two‐Photon Absorption Properties of Lanthanide Complexes Including Near‐IR Emitters

The synthesis of tris(2‐thenoyltrifluoroacetonate)lanthanide(III) complexes featuring a diethylaminostyryl‐2,2′‐bipyridine coligand was achieved for lanthanum; the near‐infrared (NIR) emitters neodymium, erbium, and ytterbium; and the transition‐metal yttrium. The photophysical properties were thoroughly studied, and it was demonstrated that the conjugated bipyridine ligand acts as a good antenna for the sensitization of the NIR emitters. The two‐photon absorption (TPA) properties of all five complexes were investigated by using both two‐photon excited fluorescence and the Z‐scan method. We demonstrate that the nature of the rare earth ion has almost no influence on the TPA properties centered on the conjugated bipyridyl ligand. Finally, we show that Yb^III is sensitized by a two‐photon antenna effect, and that Nd^III is mostly sensitized by a one‐photon process involving direct excitation of forbidden f–f transitions.     

Ring-opening metathesis polymerization (ROMP) of isomerically pure functional monomers and acyclic diene metathesis depolymerization (retro-ADMET) of functionalized polyalkenamers

ROMP and retro-acyclic diene metathesis (ADMET) were used for the synthesis of new functional polymers and functional oligomers, respectively. Purely exo and enantiomerically pure norbornene and 7-oxanorbornene derivatives were prepared using stereospecific synthesis, effective fractionation and high yield condensation reactions. Successful ROMPs of those monomers were performed using either the new carbenic Schrock’s or Grubb’s catalysts or in some cases a classical bicomponent catalyst. New functional polymers such as optically active poly(norbornene-2-carboxylic acid), reactive poly(norbornene-2-azlactone), and side-chain liquid crystal polyoxanorbornenes were fully characterized. On the other hand, successful depolymerizations of 1,4-polyisoprene and of epoxidized 1,4-polybutadiene via cross-metathesis with 4-octene were performed using a stabilized bicomponent catalyst and the Grubb’s catalyst, respectively. Conditions for the controlled synthesis of epoxidized oligobutadienes and of epoxydienic monomers via retro-ADMET were clearly defined.     

Production of vector and tensor mesons in proton-proton collisions at\sqrt s = 52.5 GeV

Inclusive production of ?⁰,f, andg ⁰ mesons and ofK _s ⁰ ,K ^*0 (892), ? andK ^*0(1430)mesons has been measured at <y>～2.6 and <p _T >～1.1 GeV/c in proton-proton interactions at \(\sqrt s = 52.5\) GeV. The negative particle from the two-body decays of these resonances were identified by a threshold Cerenkov counter and used for triggering. Starting from the measured differential cross section, total inclusive cross sections for the vector and tensor mesons were determined using various parametrizations for they andp _T dependence of the differential cross section. The experimental results are discussed in the framework of production models based on the parton picture. The strangeness suppresion factor λ=(0.30±0.10) due toSU(3) symmetry breaking of the quark sea is derived.     

Magnetic interface polarization of the La-5d states in Fe/LaHx multilayers

For rare-earth (RE)-hydrides (REHx), a metal-to-insulator transition is observed if the hydrogen concentration is increased from the dihydride (x=2) towards the trihydride (x=3). This transition provides an object for studies of the magnetic interface polarization in layered ferromagnet/insulator structures. For different samples with a fixed Fe and varied LaH_x sublayer thickness t_LaHx ([15 ? Fe/t? LaH_x]xn), the H concentration x in the LaH_x sublayer is gradually increased in the experiment. Starting from the as prepared dihydride REH_2-δ, the modification of the magnetic polarization of the La-5d states at the Fe/La_x interface is studied across the transition by magnetic circular dichroism measurements at the La-L₂ and L₃ edges. The experiments reveal an induced magnetic polarization of the La-5d hole states on a length scale of 9 ? that is independent of the altered electronic structure of the La-5d states. Received: 23 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001