Efficient access to functionalised medium-ring systems by radical fragmentation/radical addition to α-iodoketones

Functionalised medium-ring systems of various sizes can be efficiently prepared by a novel approach that embodies a radical-induced fragmentation of bicyclic β-hydroxy ketones, followed by a second radical-coupling reaction. The unexpected reactivity of α-keto radicals is also discussed.     

Pseudohexagonal crystallinity and thermal and tensile properties of ethene–propene copolymers

Structural (X‐ray diffraction), melting (differential scanning calorimetry), as well as mechanical (tensile tests) characterizations on uncrosslinked ethene–propene copolymer samples, obtained using a metallocene‐based catalytic system and having an ethene content in the range 80–50% by mol, are reported. Samples with an ethene content in the range 80–60% by mol present a disordered pseudohexagonal crystalline phase, whose melting moves from ≈ 40°C down to ≈ −20°C as the ethene content is reduced. The dramatic influence of the crystalline phase on tensile properties of uncrosslinked ethene–propene copolymers is shown. In particular, highest elongation at break values are obtained for samples being essentially amorphous in the unstretched state and partially crystallizing under stretching. On the other hand, lowest tension set values (most elastic behavior) are observed for samples presenting, already in the unstretched state, microcrystalline domains acting as physical crosslinks in a prevailing amorphous phase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1095–1103, 1999     

Study on the enzymatic polymerization mechanism of lactone and the strategy for improving the degree of polymerization

Polymerization of several lactones were carried out by employing Pseudomonas sp. lipase as the catalyst. The data indicate that water is consumed at the onset of polymerization and released in part during subsequent stages, leading us to propose a complex mechanism for the enzymatic polymerization of lactone. This mechanism involves both ring‐opening and linear condensation polymerization. The former was dominant at the early stage while the latter was dominant in the later stage. In addition, the reaction media showed complex influences on enzymatic polymerization. Some organic solvents increased the degree of polymerization (DP) and decreased the molecular weight distribution. A strategy to increase the molecular weight of the polymer is introduced, which led to the synthesis of a polymer with a number‐average molecular weight (M_n) of 14,500—the highest M_n of poly(ε‐caprolactone) prepared by enzyme‐catalyzed polymerization thus far—and molecular weight distribution of 1.23. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1265–1275, 1999     

Effects of ethylene polymerization conditions on the activity of SiO2-supported zirconocene and on polymer properties

The effects of polymerization conditions were evaluated on the production of polyethylene by silica-supported (n-BuCp)₂ZrCl₂ grafted under optimized conditions and cocatalyzed by methylaluminoxane (MAO). The Al : Zr molar ratio, reaction temperature, monomer pressure, and the age and concentration of the catalyst were systematically varied. Most reactions were performed in toluene. Hexane, with the addition of triisobutilaluminum (TIBA) to MAO, was also tested as a polymerization solvent for both homogeneous and heterogeneous catalyst systems. Polymerization reactions in hexane showed their highest activities with MAO : TIBA ratios of 3 : 1 and 1 : 1 for the homogeneous and supported systems, respectively. Catalyst activity increased continuously as Al : Zr molar ratios increased from 0 to 2000, and remained constant up to 5000. The highest activity was observed at 333 K. High monomer pressures (≈ 4 atm) appeared to stabilize active species during polymerization, producing polyethylenes with high molecular weight (≈ 3 × 10⁵ g mol⁻¹). Catalyst concentration had no significant effect on polymerization activity or polymer properties. Catalyst aging under inert atmosphere was evaluated over 6 months; a pronounced reduction in catalyst activity [from 20 to 13 × 10⁵ g PE (mol Zr h)⁻¹] was observed only after the first two days following preparation. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1987–1996, 1999     

Isothermal crystallization of concentrated amorphous starch systems measured by modulated differential scanning calorimetry

The slow isothermal crystallization of concentrated amorphous starch systems is measured by Modulated Differential Scanning Calorimetry (MDSC). It can be followed continuously by the evolution (stepwise decrease) of the MDSC heat capacity signal (Cp), as confirmed with data from X-ray diffractometry, Dynamic Mechanical Analysis, Raman spectroscopy, and conventional Differential Scanning Calorimetry. Isothermal MDSC measurements enable a systematic study of the slow crystallization process of a concentrated starch system, such as a pregelatinized waxy corn starch with 24 wt % water and 76 wt % starch. After isothermal crystallization, a broad melting endotherm with a bimodal distribution is observed, starting about 10°C beyond the crystallization temperature. The bulk glass transition temperature (T_g) decreases about 15°C during crystallization. The isothermal crystallization rate goes through a maximum as a function of crystallization time. The maximum rate is characterized by the time at the local extreme in the derivative of Cp (t_max), or by the time to reach half the decrease in Cp (t_1/2). Both t_max and t_1/2 show a bell-shaped curve as a function of crystallization temperature. The temperature of maximum crystallization rate, for the system studied, lies as high as 75°C. This is approximately 65°C above the initial value of T_g. Normalized Cp curves indicate the temperature dependence of the starch crystallization mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2881–2892, 1999     

Determination of trace rare earth elements by X-ray fluorescence spectrometry after preconcentration on a new chelating resin loaded with thorin

A very stable chelating resin was prepared by adsorption of (o-[3,6-disulfo-2-hidroxy-1-naphthylazo]-benzenearsonic acid) (thorin) on a macroporous resin Amberlite XAD-7. The optimal conditions for preparing it were obtained through the study of the adsorption properties of the resin and the thermodynamic quantities of the adsorption processes. Likewise, the behavior of the loaded resin with the rare earth elements (REE) were studied (pH of retention, sorption kinetics, etc). The conditions to prepare a thin film with this system were also evaluated. The loaded resin was successfully used for the separation and preconcentration of Sm(III), Eu(III) and Gd(III) prior to their determination by X-ray fluorescence (XRF) spectrometry. The preconcentration factor obtained was 500 and the concentrations at low detection limit were 13.8, 17 and 15.7 microg l(-1) for Sm, Eu and Gd, respectively.     

Isolation from pig liver microsomes, identification by electrospray tandem mass spectrometry and in vitro immunosuppressive activity of a rapamycin tris-epoxide metabolite

It was demonstrated that rapamycin is metabolized in vitro by pig liver microsomes under the influence of the cytochrome P450-dependent mixed function oxygenase system to a rapamycin tris-epoxide metabolite, as demonstrated by electrospray tandem mass spectrometry. The in vitro immunosuppressive activity of this metabolite was found to be lower than that of rapamycin, probably because the rapamycin effector sector was structurally modified. The effector region of rapamycin was recognized to include the conjugated double bonds of this compound and metabolic reactions affecting this region may change the binding affinity of the rapamycin-FKBP binary complex towards another pharmacological receptor bound to the binary complex. Moreover, metabolic modifications in the effector region are probably able to induce a change in the binding affinities of the rapamycin-FKBP binary complex, including the pipecolic acid moiety and the lactone function of the parent drug.     

The structure characterization of dinucleoside and nucleoside glucopyranosides lipophilic phosphotriesters by fast-atom bombardment tandem mass spectrometry

Rules for the gas-phase fragmentation mechanism of the negative ions of lipophilic phosphotriester molecules of biological interest have been established by fast-atom bombardment mass spectrometry/mass spectrometry. The mass-analyzed ion kinetic energy spectra of the [M ? H]^? of dinucleoside (1–4) and nucleoside glucopyranoside (5–9) phosphotriesters show that in the absence of charges on the phosphate bridge, the availability of acidic protons on the 5′-end nucleobase drives a preferred reaction path which leads to 5′-O-nucleotide or 6-O-glucopyranoside monophosphate anions.     

Development and validation of an analytical method for detection of estrogens in water

An analytical procedure enabling routine analysis of four environmental estrogens at concentrations below 1 ng L^–1 in estuarine water samples has been developed and validated. The method includes extraction of water samples using solid-phase extraction discs and detection by gas chromatography (GC) with tandem mass spectrometry (MS–MS) in electron-impact (EI) mode. The targeted estrogens included 17- and 17-estradiol (aE2, bE2), estrone (E1), and 17-ethinylestradiol (EE2), all known environmental endocrine disruptors. Method performance characteristics, for example trueness, recovery, calibration, precision, accuracy, limit of quantification (LOQ), and the stability of the compounds are presented for each of the selected estrogens. Application of the procedure to water samples from the Scheldt estuary (Belgium – The Netherlands), a polluted estuary with reported incidences of environmental endocrine disruption, revealed that E1 was detected most frequently at concentrations up to 7 ng L^–1. aE2 was detected once only and concentrations of bE2 and EE2 were below the LOQ.Presented at the 9th FECS Conference on Chemistry and the Environment, Bordeaux, France, 29 August–1 September 2004     

Rodlike bimetallic ruthenium and osmium complexes bridged by phenylene spacers. Synthesis, electrochemistry, and photophysics

In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2'-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 A for the shortest and longest complex, respectively. For one of the ruthenium precursors, [Rubpy-ph2-Si(CH3)3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed.