Vanadium(V) tetra-phenolate complexes: synthesis, structural studies and ethylene homo-(co-)polymerization capability

Reaction of α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p-xylene (p-L¹H₄) with two equivalents of [VO(OR)₃] (R = nPr, tBu) in refluxing toluene afforded, after work-up, the complexes {[VO(OnPr)(THF)]₂ (μ-p-L¹)}·2(THF) (1·2(THF)) or {[VO(OtBu)]₂ (μ-p-L¹)}·2MeCN (2·2MeCN), respectively in moderate to good yield. A similar reaction using the meta pro-ligand, namely α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-m-xylene (m-L²H₄) afforded the complex {[VO(OnPr)(THF)]₂ (μ-p-L²)} (3). Use of [V(Np-R¹C₆H₄)(tBuO)₃] (R¹ = Me, CF₃) with p-L¹H₄ led to the isolation of the oxo–imido complexes {[VO(tBuO)][V(Np-R¹C₆H₄) (tBuO)](μ-p-L¹)} (R¹ = Me, 4·CH2Cl₂; CF₃, 5·CH2Cl₂), whereas use of [V(Np-R¹C₆H₄)CL³] (R¹ = Me, CF₃) in combination with Et₃N/p-L¹H₄ or p-L¹Na₄ afforded the diimido complexes {[V(Np-MeC₆H₄)(THF)Cl]₂ (μ-p-L¹)}·4toluene (6·4toluene) or {[V(Np-CF₃C₆H₄)(THF)Cl]₂ (μ-p-L¹)} (7). For comparative studies, the complex [(VO)(μ-OnPr)L³]₂ (8) has also been prepared via the interaction of [VO(nPrO)₃] and 2-(α-(2-hydroxy-3,5-di-tert-butylphenyl)benzyl)-4,6-di-tert-butylphenol (L³H2). The crystal structures of 1·2THF, 2·2MeCN, 3, 4·CH2Cl₂, 5·CH2Cl₂, 6·4toluene·THF, 7 and 8 have been determined. Complexes 1–3 and 5–8 have been screened as pre-catalysts for the polymerization of ethylene in the presence of a variety of co-catalysts (with and without a re-activator), including DMAC (dimethylaluminium chloride), DEAC (diethylaluminium chloride), EADC (ethylaluminium dichloride) and EASC (ethylaluminium sesquichloride) at various temperatures and for the co-polymerization of ethylene with propylene; results are compared versus the benchmark catalyst [VO(OEt)Cl₂]. In some cases, activities as high as 243 400 g mmol⁻¹ V⁻¹ h⁻¹ (30.43 kgPE mmol V⁻¹ h⁻¹ bar⁻¹) were achievable, whilst it also proved possible to obtain higher molecular weight polymers (in comparable yields to the use of [VO(OEt)Cl₂]). In all cases with dimethylaluminium chloride (DMAC)/ethyltrichloroacetate (ETA) activation, the activities achieved surpassed those of the benchmark catalyst. In the case of the co-polymerization of ethylene with propylene, complexes 1–3 and 5–8 showed comparable or higher molecular weight than [VO(OEt)Cl₂] with comparable catalytic activities or higher in the case of the imido complexes 6 and 7

Mg4Sb2O9 of the ilmenite structure type

Single crystals of the title compound, tetra­magnesium dianti­monate(V), were obtained by the slow cooling method with K2CO3. The structure is isotypic with ilmenite, which is constructed by the alternate stacking of layers consisting of metal–oxygen coordination octa­hedra. In each layer, the octa­hedra are connected by sharing edges so as to make holes. One of the two non-equivalent metal sites is fully occupied by Mg (3 symmetry), while the second metal site (3 symmetry) is disordered and occupied by Mg and Sb with occupation factors of 1/3 and 2/3, respectively

Membrane-damaging action of Clostridium perfringens alpha-toxin on phospholipid liposomes

AbstractThe effect of Clostridium perfringens alpha-toxin on multilamellar liposomes prepared from various phospholipids and cholesterol was investigated. The toxin induced carboxyfluorescein leakage from liposomes composed of the choline-containing phospholipids such as egg-yolk phosphatidylcholine and bovine brain sphingomyelin in a dose-dependent manner, but did not induce leakage from those liposomes composed of bovine brain phosphatidylethanol amine, egg-yolk phosphatidylserine or phosphatidylglycerol. The toxin-induced carboxyfluorescein leakage from egg-yolk phosphatidylcholine liposomes was increased by addition of divalent cations. The toxin induced carboxyfluorescein release from liposomes composed of phosphatidylcholine containing unsaturated fatty acyl residues or shorter chain length saturated fatty acyl residues (12 or 14 carbon atoms), but did not induce such release from liposomes composed of phosphatidylcholine containing saturated fatty acyl residues of between 16 and 20 carbon atoms. Furthermore, the toxin-induced carboxyfluorescein release decreased with increasing chain length of the acyl residues of phosphatidylcholine used. The toxin bound to liposomes composed of phospholipids which are hydrolyzed by the toxin, but did not bind to those composed of phospholipids which are not attacked by the toxin. The toxin-induced carboxyfluorescein release from liposomes composed of dipalmitoleoyl-l-α-phosphatidyl-choline and cholesterol and the toxin binding to the liposomes decreased with decreasing cholesterol contents. These observations suggest that the specific binding site formed by the choline-containing phospholipids and cholesterol, and membrane fluidity in liposomes are essential for the membrane-damaging activity of alpha-toxin

A new sensor system for simultaneously detecting the position and incident angle of a light spot

The present paper describes a newly devised sensor, which has the ability to detect the two-dimensional position and the one-dimensional angle of a light spot simultaneously. Ordinary laser-based measurement systems utilize CCD or PSD sensors. These conventional sensors can detect only a light spot's position. When the sensor can detect the incident angle of a light spot as well as the position, the sensor has a wide range of applicability. The sensor consists of two linear array-type sensors whose depth positions are slightly different. We have designed and built a prototype sensor system. We experimentally verified the practicable accuracy of the present sensor system. We also applied the present sensor system to two typical laser-based measurement systems: 2-D position measurement, and 3-D shape measurement for specular objects. Experimental results show that the sensor system was applicable to a laser-based measurement system. </p

Vanadium(V) oxo and imido calix[8]arene complexes: synthesis, structural studies, and ethylene homo/copolymerisation capability

Interaction of p-tert-butylcalix[8]areneH₈ (L⁸H₈) with in-situ generated [NaVO(Ot-Bu)₄] (from VOCl₃ and four equivalents of NaOtBu) afforded the dark brown complex [Na(NCMe)₅][(VO)₂L⁸H]·4MeCN (1·4MeCN), in which the calix[8]arene adopts a saddle-shaped conformation. Increasing (to four equivalents per L⁸) the amount of [NaVO(Ot-Bu)₄] present in the reaction, led to the formation of the yellow octa-vanadyl complex {[(Na(VO)₄L⁸)(Na(NCMe))₃] [Na(NCMe)₆}₂·10MeCN (2·10MeCN), in which the calix[8]arene adopts a pleated loop conformation. In the presence of adventitious oxygen, reaction of four equivalents of [VO(Ot-Bu)₃] (generated from VOCl₃ and 3KOtBu) with L⁸H₈ afforded the alkali-metal free green complex [(VO)₄L⁸(μ³-O)₂] (3); the solvates 3·3MeCN and 3·3CH₂Cl₂ have been isolated. In both solvates, the L⁸ ligand adopts a shallow saddle-shaped conformation, supporting a core comprising of a (VO)₄O₄ ladder. In the case of lithium, in order to obtain crystalline material, it was found necessary to reverse the order of addition such that lithium tert-butoxide was added to L⁸H₈, and then subsequently treated (at –78 ⁰C) with two equivalents of VOCl₃; crystallization from tetrahydrofuran (THF) afforded {(VO₂)₂Li₆[L⁸](thf)₂(OtBu)₂(Et₂O)₂}·Et₂O (4·Et₂O). In the structure of 4·Et₂O, vanadium, lithium and oxygen form a central lattern-type cage, which is capped top and bottom by an Li₂O₂2 diamond; the calix[8]arene is in a ‘down, down, out, out, down, down’ conformation. When the ‘same reaction’ was extracted into acetonitrile (MeCN), the salt complex [Li(NCMe)₄][(VO)₂L⁸H]·8MeCN (5.8MeCN) was formed. In 5·8MeCN, the [Li(NCMe)₄] cations reside between the anions in the clefts of L⁸H, the latter adopting a saddle-shaped conformation. Use of the imido precursors [V(Nt-Bu)(Ot-Bu)₃] and [V(Np-tolyl)(Ot-Bu)₃] and L⁸H₈, afforded, via an imido exchange, the salt [t-BuNH₃]{[V(p-tolylN)]₂L⁸H}·3½MeCN (6·3½MeCN). The molecular structures of 1 to 6 are reported; data collections for complexes 2·10MeCN, 3·3MeCN and 3·3CH₂Cl₂ required the use of synchrotron radiation. Complexes 1, 3 and 4 have been screened as pre-catalysts for the polymerization of ethylene in the presence of a variety of co-catalysts (with and without a re-activator) at various temperatures and for the co-polymerization of ethylene with propylene; results are compared versus the benchmark catalyst VO(OEt)Cl₂. In some cases, activities as high as 136,000 g/mmol.v.h were achievable, whilst it also proved possible to obtain higher molecular weight polymers (in comparible yields) versus the use of VO(OEt)Cl₂. In the case of the co-polymerization, the incorporation of propylene was 7.1 – 10.9 mol% (cf 10 mol% for VO(OEt)Cl₂), though catalytic activities were lower versus VO(OEt)Cl₂

A new laser-based position sensor with the ability of detecting the incident angle of a light

This paper describes a new sensor with the ability of simultaneously detecting the position and the incident angle of a light. The basic principle is to detect the difference in the peak positions between two image sensors. We have designed and build three kinds of prototype of the proposed sensor. We experimentally verified the practicable accuracy of the proposed position sensors.</p