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S.C. Snyder G.D. Lassahn 《Journal of Quantitative Spectroscopy & Radiative Transfer》2007,107(2):217-225
Direct gas temperature and gas velocity measurements made in the exit plane of a subsonic argon-hydrogen thermal plasma jet from high-resolution lineshape analysis of laser light scattered by the plasma are reported. The lineshapes are in general a superposition of the ion feature of the Thomson-scattered light and the lineshape of Rayleigh scattered light. In the center of the jet Thomson scattering dominates while at larger radii Rayleigh scattering dominates. Because of the complexity of the lineshapes of light scattered by multicomponent plasmas, only those that are predominantly due to Thomson scattering can in practice be analyzed for gas temperature. Gas velocity can be determined from the Doppler shift of the lineshapes relative to the frequency of the incident laser if the velocity is greater than about 50 m s−1. The maximum gas temperature measured was 14,500 K±5%. The maximum gas velocity measured was 1100 m s−1±3%. Temperature values and the radial velocity profile are compared with those previously obtained from a subsonic all-argon plasma jet operated under similar conditions. 相似文献
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Three 5,5'-substituted 2,2'-bipyridyl ligands around a metal atom form two clefts which can encapsulate sulfate, perchlorate, or nitrate anions. 相似文献
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Bernd Berchtold Vasile Lozan Paul‐Gerhard Lassahn Christoph Janiak 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3604-3614
Nickel(II) and palladium(II) complexes with α‐dioxime ligands dimethylglyoxime, diphenylglyoxime, and 1,2‐cyclohexanedionedioxime represent six new precatalysts for the polymerization of norbornene that can be activated with methylaluminoxane (MAO), the organo‐Lewis acid tris(pentafluorophenyl)borane [B(C6F5)3], and triethylaluminum (TEA) AlEt3. The palladium but not the nickel precatalysts could also be activated by B(C6F5)3 alone, whereas two of the three nickel precatalysts but none of the palladium systems are somewhat active with only TEA as a cocatalyst. It was possible to achieve very high polymerization activities up to 3.2 · 107 gpolymer/molmetal · h. With the system B(C6F5)3/AlEt3, the activation process can be formulated as the following two‐step reaction: (1) B(C6F5)3 and TEA lead to an aryl/alkyl group exchange and result in the formation of Al(C6F5)nEt3?n and B(C6F5)3?nEtn; and (2) Al(C6F5)nEt3?n will then react with the precatalysts to form the active species for the polymerization of norbornene. Variation of the B:Al ratio shows that Al(C6F5)Et2 is sufficient for high activation. Gel permeation chromatography indicated that it was possible to control the molar mass of poly(norbornene)s by TEA or 1‐dodecene as chain‐transfer agents; the molar mass can be varied in the number‐average molecular weight range from 2 · 103 to 9 · 105 g · mol?1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3604–3614, 2002 相似文献
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Tris(pentafluorophenyl)borane, B(C6F5)3 reacts with triethylaluminum, AlEt3 to a mixture of Al(C6F5)3−nEtn and Al2(C6F5)6−nEtn compounds depending on the B/Al ratio. From excess borane to excess AlEt3 the species Al(C6F5)3 → Al(C6F5)2Et Al2(C6F5)4Et2 → Al2(C6F5)3Et3 → Al2(C6F5)2Et4 → Al2(C6F5)Et5 are formed and differentiated by their para-F signal in 19F NMR. The reaction between B(C6F5)3 and the higher aluminum alkyls, tri(iso-butyl)aluminum and tri(n-hexyl)aluminum AlR3 (R = i-Bu, n-C6H13) is slower and requires AlR3 excess to shift the C6F5 R exchange equilibria to almost complete formation of Al(C6F5)R2 and BR3. At equimolar ratio the equilibrium lies on the side of the unchanged borane together with its boranate [B(C6F5)3R]− anion. For tri(n-octyl)aluminum even at large Al(n-C8H17)3 excess no C6F5 alkyl exchange can be observed, but boranate anions form. 相似文献
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Theurillat R Knobloch M Schmitz A Lassahn PG Mevissen M Thormann W 《Electrophoresis》2007,28(15):2748-2757
CE with multiple isomer sulfated beta-CD as the chiral selector was assessed for the simultaneous analysis of the enantiomers of ketamine and metabolites in extracts of equine plasma and urine. Different lots of the commercial chiral selector provided significant changes in enantiomeric ketamine separability, a fact that can be related to the manufacturing variability. A mixture of two lots was found to provide high-resolution separations and interference-free detection of the enantiomers of ketamine, norketamine, dehydronorketamine, and an incompletely identified hydroxylated metabolite of norketamine in liquid/liquid extracts of the two body fluids. Ketamine, norketamine, and dehydronorketamine could be unambiguously identified via HPLC fractionation of urinary extracts and using LC-MS and LC-MS/MS with 1 mmu mass discrimination. The CE assay was used to characterize the stereoselectivity of the compounds' enantiomers in the samples of five ponies anesthetized with isoflurane in oxygen and treated with intravenous continuous infusion of racemic ketamine. The concentrations of the ketamine enantiomers in plasma are equal, whereas the urinary amount of R-ketamine is larger than that of S-ketamine. Plasma and urine contain higher S- than R-norketamine levels and the mean S-/R-enantiomer ratios of dehydronorketamine in plasma and urine are lower than unity and similar. 相似文献
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A full literature and patent account (about 100 references) is given on work describing vinyl polymerization to form the homopolymer poly(norbornene). The interest in vinyl‐poly(norbornene) is driven by its dielectric and mechanical properties for the technical application as an interlevel dielectric in microelectronics applications. For comparison, the norbornene/olefin copolymerization is discussed also. The metal catalysts are introduced and important polymer product properties are emphasized. The six possible isomers for stereoregular poly(norbornene) are presented. 相似文献
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Two new cadmium(II)–terephthalate complexes, ∞1{[Cd2(μ-terephthalate)2(L1)2]·9H2O} (1) and [{Cd(H2O)(L2)}2(μ-terephthalate)](terephthalate) · 10H2O (2), where L1 = (E)-N1,N1-diethyl-N2-(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine; L2 = N,N′-bis-(1-pyridin-2-yl-ethylidene)-ethane-1,2-diamine; have been synthesized by a conventional solution method. Characterization by single crystal X-ray crystallography shows that compound 1 is composed of 1-D polymeric zig-zag chains with distorted pentagonal-bipyramidal cadmium centers. Compound 2 consists of centrosymmetric dinuclear complexes with a distorted pentagonal-bipyramidal cadmium center in which one terephthalate ligand bridges the metal centres and another terephthalate anion with water of crystallization forms a H-bonding network. 相似文献
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Stoppacher N Zeilinger S Omann M Lassahn PG Roitinger A Krska R Schuhmacher R 《Rapid communications in mass spectrometry : RCM》2008,22(12):1889-1898
The present study describes the liquid chromatography/tandem mass spectrometry (LC/MS/MS)-based screening and characterisation of linear antibiotic alpha-aminoisobutyric acid (Aib)-containing non-ribosomal peptides (NRP) in culture samples of the filamentous fungus Trichoderma atroviride ATCC 74058. Fungal culture filtrates were enriched by solid-phase extraction (SPE) and separated by reversed-phase high-performance liquid chromatography (HPLC), prior to mass spectrometric (MS) and tandem mass spectrometric (MS/MS) analysis on a triple quadrupole-linear ion trap tandem mass spectrometer. A workflow consisting of two alternative screening strategies was applied to search for NRP. Various MS full scan and MS/MS measurement modes led to the identification of 16 trichorzianines and diagnostic in-source fragment ions of another four trichorzianines. Furthermore, we detected 15 novel Aib-containing peptides with putative molecular weights ranging from 951.7 to 1043.7 g/mol (monoisotopic masses), composed of up to 9 amino acids. While the amino acid sequences of the novel peptaibiotics showed typical microheterogeneity and consisted of the amino acids Leu/Ile, Aib, Ser, Val/Iva, Gly, Ac-Aib, Tyr and Phe, the mass increments at the C-termini of the peptides were not assignable to any residues described in the literature. The amino acid sequences were confirmed and structure proposals made for both molecule termini by high-resolution MS and MS/MS analysis. We propose the group name 'trichoatrokontins' for the newly identified peptaibiotics. As no other peptaibiotics were found in the culture samples, the peptaibiome of the investigated strain of T. atroviride consists of at least 20 trichorzianines and 15 trichoatrokontins. 相似文献