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排序方式: 共有119条查询结果,搜索用时 187 毫秒
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Dipl.‐Chem. Vikas Aggarwal Dipl.‐Chem. Linus F. Reichenbach Dipl.‐Chem. Mirja Enders Dr. Thierry Muller Dipl.‐Ing. Simone Wolff Marlene Crone Prof. Dr.‐Ing. Michael Türk Prof. Dr. Stefan Bräse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12794-12799
The optimized synthesis of a range of cyclooctadiene‐stabilized Pt complexes that contained different perfluoro‐alkane chains, [Pt(cod)Me(CnF2n+1)], is presented. These metal–organic compounds were employed in the so‐called supercritical fluid reactive deposition (SFRD) in CO2 under reductive conditions to generate metallic nanoparticles on aluminum oxide as a porous support. Thus, Al2O3‐supported Pt nanoparticles with a narrow particle‐size distribution were obtained. At a reduction pressure of 15.5 MPa and a temperature of 353 K, particle diameters of d50=2.3–2.8 nm were generated. Decreasing the pressure during the reduction reaction led to slightly larger particles whilst decreasing the amount of organometallic precursor in CO2 yielded a decrease in the particle size from x50=3.2 nm to 2.6 nm and a particle‐size distribution of 2.2 nm. Furthermore, substitution of the CH3 end group by the CnF2n+1 end groups led to a significant drop in Pt loading of about 50 %. Within the series of perfluorinated end groups that were considered, the Pt complex that contained a branched perfluoro‐isopropyl group showed the most‐interesting results when compared to the control precursor, [Pt(cod)Me2] ( 1 ). 相似文献
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Karl-Robert Deibel Fabian KaiserRemo Zimmermann Linus MeierPeter Bolt Konrad Wegener 《Ultrasonics》2014
Ultrasonic vibration assisted cutting is a complex process with high dynamics. The interaction between cutting tool and workpiece is of key interest to understand the entire process. Experimental investigations are limited by the dynamics of the measurement system, and thus appropriately modeling of the ultrasonic vibration assisted cutting process is essential. In this investigation, a dynamic model regarding the ultrasonic vibration assisted guillotining of stacked paper sheets is developed. A Kelvin–Voigt material model, representing the individual sheets, is chosen, with its stiffness and damping parameters being empirically determined. A novel measurement strategy for studying the contact time and interaction between cutting tool and workpiece is introduced. It allows the verification of the highly dynamic behavior of the developed model. With the dynamic model, the experimentally observed cutting forces can be calculated. It is found that the dynamic forces cause a quicker failure of the material, which leads to a lower compression of the stack prior to reaching the critical cutting force. 相似文献
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A novel experimental approach using the rotating sample system (RSS) is proposed here for the determination of the critical micelle concentration (CMC) of surfactants. The RSS has been conceived in our laboratory as a convection platform for physicochemical studies and analyses in microliter-sized sample drops. The scheme allows for vigorous rotation of the drop despite its small size through efficient air-liquid mechanical coupling. Thus, changes in surface properties of aqueous samples result in corresponding modulation of the hydrodynamic performance of the RSS, which can be utilized to investigate interfacial phenomena. In this work, we demonstrate that the RSS can be used to study the effects of surfactants on the surface and in the bulk of very small samples with hydrodynamic electrochemistry. Potassium ferrocyanide is employed here with cyclic voltammetry to probe the air-water interface of solutions containing Triton X-100. The CMC of this surfactant determined using this approach is 140 ppm, which agrees well with reported values obtained with conventional methods in much larger samples. The results also demonstrate that besides the CMC, variations in bulk rheological properties can also be investigated in very small specimens using the RSS with a simple method. 相似文献
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Background
All known attempts to isolate and characterize mammalian class V alcohol dehydrogenase (class V ADH), a member of the large ADH protein family, at the protein level have failed. This indicates that the class V ADH protein is not stable in a non-cellular environment, which is in contrast to all other human ADH enzymes. In this report we present evidence, supported with results from computational analyses performed in combination with earlier in vitro studies, why this ADH behaves in an atypical way.Results
Using a combination of structural calculations and sequence analyses, we were able to identify local structural differences between human class V ADH and other human ADHs, including an elongated β-strands and a labile α-helix at the subunit interface region of each chain that probably disturb it. Several amino acid residues are strictly conserved in class I–IV, but altered in class V ADH. This includes a for class V ADH unique and conserved Lys51, a position directly involved in the catalytic mechanism in other ADHs, and nine other class V ADH-specific residues.Conclusions
In this study we show that there are pronounced structural changes in class V ADH as compared to other ADH enzymes. Furthermore, there is an evolutionary pressure among the mammalian class V ADHs, which for most proteins indicate that they fulfill a physiological function. We assume that class V ADH is expressed, but unable to form active dimers in a non-cellular environment, and is an atypical mammalian ADH. This is compatible with previous experimental characterization and present structural modelling. It can be considered the odd sibling of the ADH protein family and so far seems to be a pseudoenzyme with another hitherto unknown physiological function.50.
Johannissen LO Hay S Scrutton NS Sutcliffe MJ 《The journal of physical chemistry. B》2007,111(10):2631-2638
Hydrogen transfer, an essential component of most biological reactions, is a quantum problem. However, the proposed role of compressive motion in promoting enzymatic H-transfer is contentious. Using molecular dynamics simulations and density functional theory (DFT) calculations, we show that, during proton tunneling in the oxidative deamination of tryptamine catalyzed by the enzyme aromatic amine dehydrogenase (AADH), a sub-picosecond promoting vibration is inherent to the iminoquinone intermediate. We show by numerical modeling that this short-range vibration, with a frequency of approximately 165 cm-1, is consistent with "gating" motion in the hydrogen tunneling model of Kuznetsov and Ulstrup (Kuznetsov, A. M.; Ulstrup, J. Can. J. Chem. 1999, 77, 1085) in an enzymatic reaction with an observed protium/deuterium kinetic isotope effect that is not measurably temperature-dependent. 相似文献