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61.
Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities 总被引:11,自引:0,他引:11
Bollmann A Blann K Dixon JT Hess FM Killian E Maumela H McGuinness DS Morgan DH Neveling A Otto S Overett M Slawin AM Wasserscheid P Kuhlmann S 《Journal of the American Chemical Society》2004,126(45):14712-14713
Linear alpha-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system. 相似文献
62.
Investigation of potential-sensitive fluorescent dyes for application in nitrate sensitive polymer membranes 总被引:2,自引:0,他引:2
Gerhard J. Mohr Frank Lehmann Ralf Östereich Ivana Murkovic Otto S. Wolfbeis 《Analytical and bioanalytical chemistry》1997,357(3):284-291
The applicability of various potential-sensitive dyes (PSD) for optical sensing of anions is reported. Specifically, nitrate-responsive
polymer membranes have been developed which are composed of a plasticized polymer, an anion exchange catalyst, and a fluorescent
dye. On exposure to nitrate, the fluorescence intensity of such membranes increases, while the wavelengths of the excitation
and emission maxima remain virtually unchanged. The membranes typically are 2–4 μm thick and exhibit highest sensitivity to
nitrate in the 2 to 200 mgl–1 range. Signal changes on exposure to 100 mmol/l nitrate can be as high as +300%. The detection limit is 0.2 mgl–1. The cationic PSD octadecyl acridine organe was tested in combination with a tin-organic and an indium-organic anion carrier
rather than with tridodecylmethylammonium chloride, but both carriers were found to display no improved selectivity.
Received: 2 December 1995 / Revised: 28 March 1996 / Accepted: 5 April 1996 相似文献
63.
7-Substituted 4-hydroxycoumarins (2a-e) and 4-hydroxy-2-quinolones (2f-i) have been synthesized from the appropriate phenols or anilines and were converted to the enamines 3 using triethoxymethane and aniline. Condensation of 3 with nitriles 4a-h gave substituted 2H,5H-pyrano[3,2-c]benzopyran-2,5-diones (5a-r) or 2H,5H-pyrano[3,2-c]quinoline-2,5-diones (5s-x) , which exhibit both spontaneous and stimulated fluorescence with maxima between 418 and 549 nm. The marked influence of an electron withdrawing 3-substituent in 5 is demonstrated by the fluorescence spectra of 7a,b (synthesized from 2d,e and ethyl 3-oxobutyrate), whose maxima are sharply shifted to the blue as compared with compounds 21-r. 相似文献
64.
Wyss HM Innerlohinger J Meier LP Gauckler LJ Glatter O 《Journal of colloid and interface science》2004,271(2):388-399
The aggregation of concentrated aqueous silica suspensions is characterized by means of static light scattering. We use an in situ destabilization mechanism based on the enzyme-catalyzed hydrolysis of urea. This method enables us to continuously and homogeneously change the interparticle potential from repulsive to attractive without disturbing the aggregation process. Moreover, our electrostatically stabilized suspensions can be destabilized by two different methods. In the first method, the pH is shifted toward the isoelectric point of the particles ( Delta pH method), thereby leading to a decrease of their surface charge. In the second method, the ionic strength is continuously increased at constant pH ( Delta I method), leading to a compression of the electrical double layer around the charged particles. A laboratory-built flat-cell light-scattering instrument is used, which allows fast data acquisition and an adjustment of the sample cell thickness. To circumvent multiple scattering effects, we use a very small sample thickness ( approximately 13 microm). In addition, the refractive index difference between the aqueous phase and the particles is reduced by adding sucrose to the liquid phase of our suspensions. We are able to characterize the structural changes at the very early stages of the destabilization process, where no significant effects are yet detected in macroscopic rheological measurements. While during the Delta pH destabilization, the scattering curve shows significant changes only after some characteristic delay time, it changes continuously during the Delta I destabilization. The latter is attributed to the formation of a weak pre-gel structure in the suspensions, as a shallow secondary minimum appears in the interparticle potential. Data are evaluated by using a HMSA square-well structure factor model. Results are in good agreement with those predicted from DLVO theory. 相似文献
65.
Frank Herwig Köhler Hans Jürgen Kalder Ernst Otto Fischer 《Journal of organometallic chemistry》1975,85(2):C19-C22
Carbon-13 NMR data are reported for trimethyltin derivatives containing ERn groups where E C, Si, Ge, Sn, N, O and S including a series of cyclic amines with ring sizes from three to seven. Coupling constant values for the homologous series of fourth group derivatives give goood correlations with the electronegativity of E. The observation of the two-bond, ¦ 2J(119SnE13C) ¦ couplings only in the derivatives containing bulky R groups is rationalized by a bimolecular exchange of ERn groups in the concentrated solutions studied. 相似文献
66.
Bekers O op den Buijsch RA de Vries JE Wijnen PA van Dieijen-Visser MP 《Electrophoresis》2002,23(12):1878-1881
We describe the application of capillary electrophoresis to detect DNA fragments, obtained after amplifying a part of the apolipoprotein E (apoE) gene with polymerase chain reaction (PCR). Compared to conventional agarose slab gel electrophoresis (AGE), CE appears the method of choice with regard to resolution and sensitivity, to detect DNA fragments in the range of 20-100 base pairs. Especially discrimination between apoE2/E2 and apoE2/E3 genotypes is more reliable with CE than with AGE, this being of great clinical value in the diagnosis of familiary dysbetalipoproteinemia. 相似文献
67.
Dipole moments of seven molecules were studied by AM1, each containing an intramolecular hydrogen bond between a hydroxyl group and a carbonyl or nitro group as hydrogen acceptors. The hydrogen bond causes two electron shifts: from H to O within the hydroxyl group and from C to O within the carbonyl group. The latter is accompanied by withdrawal of electrons from even more distant atoms. If the total electron density change is expressed as a vector, its direction is close to the direction of the O-H bond. This electron redistribution is in agreement with the previous, somewhat, puzzling experimental results. However, it differs from the commonly accepted picture according to which electron density changes on the hydrogen acceptor moiety are less important than those on the O-H bond.Dedicated to Professor Viktor Gutmann on the occasion of his 70th birthday. 相似文献
68.
Trimethylsilyl Derivatives of Vb Elements. VII. Crystal Structures of Lithium Bis(trimethylsilyl)bismuthide · DME and of Tetrakis(trimethylsilyl)dibismuthane as well as Some Comments on the Crystal Structure of Bis(4-methoxyphenyl)ditellane Colourless lithium bis(trimethylsilyl)bismuthide · DME 1 1,2-Dimethoxyethan (DME); Tetrahydrofuran (THF) 1 and green, metallic lustrous tetrakis(trimethylsilyl)dibismuthane 2 crystallize isotopic to their antimony homologues [1, 2]. As it is shown by crystal structure determinations { 1 : ?90°C; I 4 2d; a = 1017,3(4); c = 3738,0(26) pm; Z = 8; R w = 0,065; 2 : + 20°C; P2 1 /c; a = 680,9(4); b = 1704,8(13); c = 1197,9 (10) pm; β = 119,46(6)°; Z = 2; R w = 0,084} both compounds form chains which in the case of bismuthide 1 are built up as screws of alternating bismuth and lithium atoms; bonding further to two trimethylsilyl groups or to the chelating DME ligand both atoms gain coordination number 4 {Li? Bi 292(3); Bi? Si 263.3(14) pm; Bi? Li? Bi 132(1); Li? Bi? Li 148(1); φ(Li? Bi? Li? Bi) 83°}. In the case of dibismuthane 2 the centrosymmetric molecules are strung, their Bi-Bi groups forming nearly linear zigzag chains with shortened intermolecular contact distances {Bi-Bi 303.5(3); Bi …? Bi 380.4(3); Bi? Si 268 pm; Bi? Bi …? Bi 169; Bi? Bi? Si 97.4(5) and 92.0(5)°}. Structure and properties of 2 are compared with those of similar compounds; the crystal structure of brown, green metallic lustrous bis(4-methoxyphenyl)ditellane 5 already published by Ludlow and McCarthy[3] is reinvestigated with respect to very short intermolecular Te…?Te contacts. 相似文献
69.
Otto Vogl Jan Bartus Joseph R. Murdoch 《Monatshefte für Chemie / Chemical Monthly》1990,121(4):311-316
Summary We report techniques for measuring optical rotation of suspended solids, including dissymmetric molecular crystals (e.g. sodium chlorate and bromate), synthetic polymers, polypeptides and biopolymers. Examples include poly(triphenylmethyl methacrylate), poly-S-lactide, poly-L-hydroxyproline, hemocyanine, cellulose acetate andRNA. The results indicate that optical rotation measurements are sensitive to differences in secondary structure and can serve as a probe for structural differences between solid-state and solution.
Messung der optischen Rotation von Makromolekülen im Festzustand unter Verwendung von Pulversuspensionen
Zusammenfassung Es wird über eine Methode zur Messung der optischen Rotation von Festkörpern in Suspensionen berichtet, wobei dissymetrische Kristalle (z. B. Natriumchlorat und -bromat), synthetische Polymere, Polypeptide und Biopolymere behandelt werden. Die Beispiele umfassen Poly(triphenylmethylmethacrylat), Poly-S-lactid, Poly-L-hydroxyprolin, Hemocyanin, Celluloseacetat undRNA. Die Ergebnisse zeigen, daß die optischen Rotationen bezüglich Unterschiede in der Sekundärstruktur empfindlich sind und daß diese Messungen als ein Maß für Strukturunterschiede zwischen Festzustand und Lösung herangezogen werden können.相似文献
70.
Jimmy Orjala Anthony D. Wright Clemens A. J. Erdelmeier Otto Sticher Topul Rali 《Helvetica chimica acta》1993,76(4):1481-1488
Five New unusual monoterpene-substituted dihydrochalcones, the adunctins A–E (1″S)-1-{2′-hydroxy-4′-methoxy-6′-[4″-methyl-1″-(1?-methylethyl)cyclohex-3″ -en-1″ -yloxy]phenyl}-3-phenylpropan-1-one ( 1 ), (5aR*,8R*,9aR*)-3-phenyl-1-[5′,8′,9′,9′a-tetrahydro-3′-hydroxy-1′-methoxy-8′-(1″-methylethyl)-5′-a-methyldibenzo-[b,d]furan-4′-yl]propan-1-one ( 2 ), (2′R*,4″S*)-1-{6′-hydroxy-4′-methoxy-4″-(1?-methylethyl)spiro[benzo[b]-furan-2′(3′H),1″ -cyclohex-2″ -en]-7′-yl}-3-phenylpropan-1-one ( 3 ), (2′R*,4″R*)-1-{6′-hydroxy-4′-methylethyl-4″-(1?-methylethyl)spiro[benzo[b]furan-2′(3′H),1″-cyclohex-2″-en]-7′-yl}-3-phenypropan-1-one ( 4 ), and (5′aR*,6′S*, 9′R*,9′aS*)-1-[5′a,6′,7′,8′,9′a-hexahydro-3′,6′-methoxy-6′-methyl-9′-(1″-methylethyl)dibenzo[b,d]-furan-4′-yl]-3-phenylpropan-1-one ( 5 ) were isolated from the leaves of Piper aduncum (Piperaceae) by preparative liquid chromatography. In addition, (?)-methyllindaretin ( 6 ), trans-phytol, and α-tocopherol ( = vitamin E) were also isolated and identified. The structures were elucidated by spectroscopic methods, including 1D- and 2D-NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The antibacterial and cytotoxic potentials of the isolates were also investigated. 相似文献