Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Combined charge and spin density experimental study of the yttrium(III) semiquinonato complex Y(HBPz3)2(DTBSQ) and DFT calculations

High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring.     

Utilisation de l'acide phénylarsonique en turbidimétrie: Dosage du tantale

A turbidimetric method is described for the determination of tantalum with phenylarsonic acid. The method is fast and rarely requires preliminary separation. The only interfering elements are zirconium and niobium when present in molar ratios greater than Nb : Ta = 1 and Zr : Ta = 5.     

Unexpected cross-coupling reaction between o-chloroaryl ketones and organomanganese reagents

Alkyl- and arylmanganese reagents react with o-chloro or o-bromoaryl ketones to give the substituted ketones in high yields. The cross-coupling reaction is performed under mild conditions (-60 to +40 degrees C, 30 min to 4 h) and takes place with excellent chemoselectivity. [reaction: see text]     

Simultaneous quantitative measurement of a new platelet activating factor antagonist (BN 50730) and its two main metabolites in human plasma and urine by LC-MS

Summary A simple and sensitive assay has been developed for the quantitative measurement of a new platelet activating factor antagonist (BN50730), and its two main metabolites (BN50727 and BN50922), at the picomole level in human plasma and urine. The three compounds of interest and the internal standard (BN50765) were measured by combined LC-negative chemical ionization MS. A simple solid-liquid extraction procedure was used to isolate the parent drug and the two metabolites. The MS was tuned to monitor the intense ionm/z 333 generated in the ion source by a dissociative capture process. The assay was on 1 ml plasma or 0.1 ml urine and the quantitation limit was calculated as 1 ng·ml^–1. The very low relative standard deviations and mean percentages of error calculated for within-day or between-day repeatability assays demonstrate the ruggedness of the technique for routine determination in biological fluids. Some preliminary results on the pharmacokinetics of the parent drug and its two main metabolites illustrate the applicability of this method.     

A shell model for tyre belt vibrations

We present a new formulation for the prediction of tyre belt vibrations in the frequency range 0-500 Hz. Our representation includes the effects of belt width, curvature and anisotropy, and also explicitly models the tyre sidewalls. Many of the associated numerical parameters are fixed by physical considerations; the remainder require empirical input. A systematic and general approach to this problem is developed, and illustrated for the specific example of a Goodyear Wrangler tyre. The resulting predictions for the radial response to radial forcing show good correspondence with experiment up to 300 Hz, and satisfactory agreement up to 1 kHz.     

Commercial fire-retarded PET formulations - Relationship between thermal degradation behaviour and fire-retardant action

Many types of fire retardants are used in poly(ethylene terephthalate), PET, formulations, and two commercial fire retardants, Ukanol^® and Phosgard^®, have been shown to improve significantly PET flame-retardancy when used as comonomers. Phosgard incorporates a phosphorus atom within the main chain whereas Ukanol incorporates a phosphorus atom as a pendent substituent. Despite their acknowledged effectiveness, the mode of action of these fire retardants remains unclear, and in this paper we present a comparison of the overall thermal degradation behaviour of PET and Ukanol and Phosgard fire-retarded formulations. DSC and particularly TGA data show that both Ukanol and Phosgard have some stabilising influence on PET degradation, especially under oxidative conditions. TGA and pyrolysis experiments both clearly indicate that neither of the additives acts as a char promoter. Only the Phosgard formulation shows any release of volatile phosphorus species which could act in the gas phase. On the other hand, the most striking feature of the pyrolysis experiments is the macroscopic structure of the chars produced by the fire-retarded formulations, which hints at their fire-retardancy action - an open-cell charred foam was obtained upon charring at 400 °C or 600 °C. This foaming layer between the degrading melt and the flame would lower the amount of fuel available for combustion, and would also limit the feedback of heat to the condensed phase.     

Compact 10-GHz Nd:GdVO4 laser with 0.5-W average output power and low timing jitter

We demonstrate a compact, diode-pumped Nd:GdVO4 laser with a repetition rate of 9.66 GHz and 0.5-W average output power. The laser is passively mode locked with a semiconductor saturable absorber mirror (SESAM), yielding 12-ps-long sech2-shaped pulses. For synchronization of the pulse train to an external reference clock, the SESAM is mounted on a piezoelectric transducer. With an electronic feedback loop of only a few kilohertz loop bandwidth we achieved a rms timing jitter of 146 fs (integrated from 10 Hz to 10 MHz). This is an upper limit because it is mostly limited by the measurement system. The laser setup with a simple linear cavity has a footprint of only 130 mm x 30 mm.     

NMR investigation of the structure of NiZrF6·.6H2O at low temperatures

Previous studies have shown that NiZrF₆.6H₂O can be described by an axial spin Hamiltonian with parameters g = 2.33 and $\text{D}\text{k}\text{= ?3.14}\text{K}$, and exhibits ferromagnetic ordering at T_c = 164mK. Our room temperature X-ray measurements confirm that NiZrF₆·.6H₂O is isomorphous with NiSnCl₆·.6H₂O and give lattice parameters of $\text{a = 6.55}\text{A}\text{?}$ and α = 96°09′. Proton NMR measurements show that there exist important molecular motions at room temperature and that the space group remains $\text{R}\text{3}$ down to liquid helium temperatures. The positions of all twelve protons have been determined and are found to lie on a sphere of radius 2.9 Å centered on the nickel ion.     

Essential countability of treeable equivalence relations

We establish a dichotomy theorem characterizing the circumstances under which a treeable Borel equivalence relation E is essentially countable. Under additional topological assumptions on the treeing, we in fact show that E   is essentially countable if and only if there is no continuous embedding of _E1${\mathbb{E}}_1$ into E. Our techniques also yield the first classical proof of the analogous result for hypersmooth equivalence relations, and allow us to show that up to continuous Kakutani embeddability, there is a minimum Borel function which is not essentially countable-to-one.