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91.
The influence of aluminium alkyl compounds on metallocene‐catalyzed high pressure polymerizations of ethylene has been investigated at 150 MPa and 180°C in a continuously operated autoclave. The catalysts were based on the metallocenes bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2) and diphenylmethylene (cyclopentadienylfluorenyl)zirconium dichloride (Ph2C‐(CpFlu)ZrCl2), which were preactivated outside the reactor with triisobutylaluminium (TiBA) and N,N‐dimethylanilinium tetrakis(pentafluorophenyl)borate (DMAP, [PhNHMe2][B(C6F5)4]). The concentrations of triisobutylaluminium (TiBA) and triethylaluminium (TEA) in the reactor were varied over a wide range, using a separate dosing for these two aluminium alkyl compounds. Productivity and polymer properties strongly depended on the type and the concentration of the aluminium alkyl compound used. Highest productivities and molecular weights were obtained with low concentrations of TiBA in the reactor. Up to a concentration of 30 molppm Al in the reactor, unimodal polymers were formed with M̄w/M̄n between 2 and 3. With higher aluminium concentrations the products formed contained small amounts of waxes, due to oligomerization catalyzed by the aluminium alkyl compounds. The molecular weight distributions (MWDs) of these products could be described as a superimposition of two Schulz‐Zimm distributions. All MWDs were analyzed with regard to the amount of waxes produced by ethylene oligomerization and with regard to the influence of chain transfer reactions to the aluminium. The rate constants of chain transfer to aluminium, in relation to the rate constants of insertion of ethylene, were estimated. 相似文献
92.
(Z,Z)-4,7-tridecadien-(S)-2-yl acetate: sex pheromone of Douglas-fir cone gall midge,Contarinia oregonensis 总被引:1,自引:0,他引:1
Gries R Khaskin G Gries G Bennett RG King GG Morewood P Slessor KN Morewood WD 《Journal of chemical ecology》2002,28(11):2283-2297
Our objectives were to identify and field test the sex pheromone of female Douglas-fir cone gall midge, Contarinia oregonensis (Diptera: Cecidomyiidae). Coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses of pheromone extract revealed a single compound (A) that elicited responses from male antennae. Hydrogenation of pheromone extract, followed by renewed GC-EAD analysis, revealed a new EAD-active compound with chromatographic characteristics identical to those of tridecan-2-yl acetate on five fused silica columns (DB-5, DB-210, DB-23, SP-1000, and Cyclodex-B). Syntheses, chromatography, and retention index calculations of all possible tridecen-2-yl acetates suggested that the candidate pheromone A was a tridecadien-2-yl acetate with nonconjugated double bonds. Synthetic candidate pheromone component (Z,Z)-4,7-tridecadien-2-yl acetate (Z4Z7) cochromatographed with A on all analytical columns and elicited comparable antennal activity. In GC-EAD analyses that separated the enantiomers (Z,Z)-4,7-tridecadien-(S)-2-yl acetate (2S-Z4Z7) and (Z,Z)-4,7-tridecadien-(R)-2-yl acetate (2R-Z4Z7) with baseline resolution, only 2S-Z4Z7 as a component in a racemic standard or in pheromone extract elicited antennal responses. In Douglas-fir seed orchards, sticky traps baited with 2S-Z4Z7 captured male C. oregonensis, whereas 2R-Z4Z7 was behaviorally benign. Comparable catches of males in traps baited with racemic Z4Z7 (50 g) or virgin female C. oregonensis suggested that synthetic pheromone baits could be developed for monitoring C. oregonensis populations in commercial Douglas-fir seed orchards. 相似文献
93.
Markus Feulner Gunter Hagen Andreas Piontkowski Andreas Müller Gerhard Fischerauer Dieter Brüggemann Ralf Moos 《Topics in Catalysis》2013,56(1-8):483-488
Diesel particulate filters (DPF) are indispensable parts of modern automotive exhaust gas aftertreatment systems due to the stringent emissions legislation. For a fuel-efficient control strategy, it would be beneficial to determine directly and in-operation their actual trapped soot mass. Two novel approaches—based on the electrical conductivity of trapped soot particles—emerged recently. By measuring the electrical resistance between different single walls inside the filter, the soot load is determined with local resolution. The microwave-based technique is a contactless approach that gives an integral value depending on the soot mass in the DPF. We present investigations on loading and regeneration of DPFs in a dynamometer test bench applying both methods. The results are compared with each other and correlated with the differential pressure and the soot mass. Especially the microwave-based technique has a potential for serial application. 相似文献
94.
Particulates give great concern for mankind health. Especially the nano size particles are under discussion. Therefore, the particle size distribution from the combustion chamber to tail pipe emissions are of great interest. With the aim of scanning mobility particle sizer the number weighted particle size distributions were measured in the combustion chamber as well as in the exhaust gas up and downstream of aftertreatment systems. Using the identical particle measurement technique results can be compared without changing the particle size definition. The particles in the cylinder of a modern serious DI diesel engine were sampled with a time resolved fast gas sampling valve. The Soot particles formed in the cylinder during the early combustion phase are oxidized by about 99% in the late combustion/early expansion phase, whereas the soot particle sizes distribution in the cylinder at the end of the expansion phase are equal to that in the tail pipe. DI diesel engines with high pressure injection system emit less numbers of particle with in tendency greater sizes compared to IDI diesel engines. Oxidation catalysts do not influence particle size distribution but particulate traps reduce particle number by up to two orders of magnitude. Detail analysis shows that an increase of nano size particle number downstream of an aftertreatment device results from artifacts. 相似文献
95.
96.
Camille Descour Tamara Meijer-Vissers Tibor Macko Matthew Parkinson Dario Cavallo Martin van Drongelen Gerhard Hubner Han Goossens Robbert Duchateau 《Polymer》2012,53(15):3096-3106
The zirconium acetamidinate catalyst {Cp*Zr(Me)2[N(Et)C(Me)N(tBu)]} (Cp* = ?5-C5Me5) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched α-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions. 相似文献
97.
98.
The Use of Thermodynamic and Kinetic Data in Drug Discovery: Decisive Insight or Increasing the Puzzlement? 下载免费PDF全文
Prof. Dr. Gerhard Klebe 《ChemMedChem》2015,10(2):229-231
The prime property to rate the success of hit‐to‐lead‐to‐drug optimization in drug discovery is binding affinity. Rational approaches try to relate this property with structure. Affinity can be linked to the thermodynamic property, Gibbs free energy of binding, which itself factorizes into enthalpy and entropy. With respect to kinetic properties, affinity can be associated with the ratio of koff and kon of complex formation. Do these features help to obtain better insight into affinity? The present viewpoint assesses our current understanding of thermodynamics– or kinetics–structure relationships and questions the accuracy of data collected to learn about the thermodynamic and kinetic basis to comprehend affinity. 相似文献
99.
One Question,Multiple Answers: Biochemical and Biophysical Screening Methods Retrieve Deviating Fragment Hit Lists 下载免费PDF全文
Dr. Johannes Schiebel Nedyalka Radeva Dr. Helene Köster Dr. Alexander Metz Timo Krotzky Dr. Maren Kuhnert Prof. Wibke E. Diederich Prof. Andreas Heine Dr. Lars Neumann Dr. Cedric Atmanene Dominique Roecklin Dr. Valérie Vivat‐Hannah Dr. Jean‐Paul Renaud Dr. Robert Meinecke Dr. Nina Schlinck Dr. Astrid Sitte Franziska Popp Dr. Markus Zeeb Prof. Gerhard Klebe 《ChemMedChem》2015,10(9):1511-1521
Fragment‐based lead discovery is gaining momentum in drug development. Typically, a hierarchical cascade of several screening techniques is consulted to identify fragment hits which are then analyzed by crystallography. Because crystal structures with bound fragments are essential for the subsequent hit‐to‐lead‐to‐drug optimization, the screening process should distinguish reliably between binders and non‐binders. We therefore investigated whether different screening methods would reveal similar collections of putative binders. First we used a biochemical assay to identify fragments that bind to endothiapepsin, a surrogate for disease‐relevant aspartic proteases. In a comprehensive screening approach, we then evaluated our 361‐entry library by using a reporter‐displacement assay, saturation‐transfer difference NMR, native mass spectrometry, thermophoresis, and a thermal shift assay. While the combined results of these screening methods retrieve 10 of the 11 crystal structures originally predicted by the biochemical assay, the mutual overlap of individual hit lists is surprisingly low, highlighting that each technique operates on different biophysical principles and conditions. 相似文献
100.
Structural Determinants of the Selectivity of 3‐Benzyluracil‐1‐acetic Acids toward Human Enzymes Aldose Reductase and AKR1B10 下载免费PDF全文
Dr. Francesc X. Ruiz Alexandra Cousido‐Siah Dr. Sergio Porté Dr. Marta Domínguez Isidro Crespo Chris Rechlin Dr. André Mitschler Prof. Dr. Ángel R. de Lera Dr. María Jesús Martín Dr. Jesús Ángel de la Fuente Prof. Dr. Gerhard Klebe Prof. Dr. Xavier Parés Prof. Dr. Jaume Farrés Dr. Alberto Podjarny 《ChemMedChem》2015,10(12):1989-2003
The human enzymes aldose reductase (AR) and AKR1B10 have been thoroughly explored in terms of their roles in diabetes, inflammatory disorders, and cancer. In this study we identified two new lead compounds, 2‐(3‐(4‐chloro‐3‐nitrobenzyl)‐2,4‐dioxo‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0048, 3 ) and 2‐(2,4‐dioxo‐3‐(2,3,4,5‐tetrabromo‐6‐methoxybenzyl)‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0049, 4 ), which selectively target these enzymes. Although 3 and 4 share the 3‐benzyluracil‐1‐acetic acid scaffold, they have different substituents in their aryl moieties. Inhibition studies along with thermodynamic and structural characterizations of both enzymes revealed that the chloronitrobenzyl moiety of compound 3 can open the AR specificity pocket but not that of the AKR1B10 cognate. In contrast, the larger atoms at the ortho and/or meta positions of compound 4 prevent the AR specificity pocket from opening due to steric hindrance and provide a tighter fit to the AKR1B10 inhibitor binding pocket, probably enhanced by the displacement of a disordered water molecule trapped in a hydrophobic subpocket, creating an enthalpic signature. Furthermore, this selectivity also occurs in the cell, which enables the development of a more efficient drug design strategy: compound 3 prevents sorbitol accumulation in human retinal ARPE‐19 cells, whereas 4 stops proliferation in human lung cancer NCI‐H460 cells. 相似文献