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Daniel Stubba Dr. Dennis Bensinger Janika Steinbacher Lilia Proskurjakov Álvaro Salcedo Gómez Dr. Uwe Schmidt Prof. Dr. Stefan Roth Prof. Dr. Katja Schmitz Prof. Dr. Boris Schmidt 《ChemMedChem》2019,14(23):2005-2022
The ubiquitin-proteasome system (UPS) is an established therapeutic target for approved drugs to treat selected hematologic malignancies. While drug discovery targeting the UPS focuses on irreversibly binding epoxyketones and slowly-reversibly binding boronates, optimization of novel covalent-reversibly binding warheads remains largely unattended. We previously reported α-ketoamides to be a promising reversible lead motif, yet the cytotoxic activity required further optimization. This work focuses on the lead optimization of phenoxy-substituted α-ketoamides combining the structure-activity relationships from the primed and the non-primed site of the proteasome β5 subunit. Our optimization strategy is accompanied by molecular modeling, suggesting occupation of P1′ by a 3-phenoxy group to increase β5 inhibition and cytotoxic activity in leukemia cell lines. Key compounds were further profiled for time-dependent inhibition of cellular substrate conversion. Furthermore, the α-ketoamide lead structure 27 does not affect escape response behavior in Danio rerio embryos, in contrast to bortezomib, which suggests increased target specificity. 相似文献
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Daniel Ortiz Morales Simon Westerberg Pedro X. La Hera Uwe Mettin Leonid Freidovich Anton S. Shiriaev 《野外机器人技术杂志》2014,31(3):343-363
Working with forestry machines requires a great deal of training to be sufficiently skilled to operate forestry cranes. In view of this, it would be desirable within the forestry industry to introduce automated motions, such as those seen in robotic arms, to shorten the training time and make the work of the operator easier. Motivated by this fact, we have developed two experimental platforms for testing control systems and motion‐planning algorithms in real time. They correspond to a laboratory setup and a commercial version of a hydraulic manipulator used in forwarder machines. The aim of this article is to present the results of this development by providing an overview of our trajectory‐planning algorithm and motion‐control method, with a subsequent view of the experimental results. For motion control, we design feedback controllers that are able to track reference trajectories based on sensor measurements. Likewise, we provide arguments to design controllers in an open‐loop for machines that lack sensing devices. Relying on the tracking efficiency of these controllers, we design time‐efficient reference trajectories of motions that correspond to logging tasks. To demonstrate performance, we provide an overview of extensive testing done on these machines. 相似文献
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The development of innovative metal catalysis for selective bond formation is an important task in organic chemistry. The group 13 metal indium is appealing for catalysis because indium-based reagents are minimally toxic, selective, and tolerant toward various functional groups. Among elements in this group, the most stable oxidation state is typically +3, but in molecules with larger group 13 atoms, the chemistry of the +1 oxidation state is also important. The use of indium(III) compounds in organic synthesis has been well-established as Lewis acid catalysts including asymmetric versions thereof. In contrast, only sporadic examples of the use of indium(I) as a stoichiometric reagent have been reported: to the best of our knowledge, our investigations represent the first synthetic method that uses a catalytic amount of indium(I). Depending on the nature of the ligand or the counteranion to which it is coordinated, indium(I) can act as both a Lewis acid and a Lewis base because it has both vacant p orbitals and a lone pair of electrons. This potential ambiphilicity may offer unique reactivity and unusual selectivity in synthesis and may have significant implications for catalysis, particularly for dual catalytic processes. We envisioned that indium(I) could be employed as a metallic Lewis base catalyst to activate Lewis acidic boron-based pronucleophiles for selective bond formation with suitable electrophiles. Alternatively, indium(I) could serve as an ambiphilic catalyst that activates both reagents at a single center. In this Account, we describe the development of low-oxidation state indium catalysts for carbon-carbon bond formation between boron-based pronucleophiles and various electrophiles. We discovered that indium(I) iodide was an excellent catalyst for α-selective allylations of C(sp(2)) electrophiles such as ketones and hydrazones. Using a combination of this low-oxidation state indium compound and a chiral semicorrin ligand, we developed catalytic highly enantioselective allylation, crotylation, and α-chloroallylation reactions of hydrazones. These transformations proceeded with rare constitutional selectivities and remarkable diastereoselectivities. Furthermore, indium(I) triflate served as the most effective catalyst for allylations and propargylations of C(sp(3)) electrophiles such as O,O-acetals, N,O-aminals, and ethers, and we applied this methodology to carbohydrate chemistry. In addition, a catalyst system composed of indium(I) chloride and a chiral silver BINOL-phosphate facilitated the highly enantioselective allylation and allenylation of N,O-aminals. Overall, these discoveries demonstrate the versatility, efficiency, and sensitivity of low-oxidation state indium catalysts in organic synthesis. 相似文献
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Raqibul Mostafa Ramesh C. Pallat Uwe Ringel Ashok A. Tikku Jeffrey H. Reed 《ETRI Journal》2012,34(3):319-329
Closed‐loop transmit diversity is considered an important technique for improving the link budget in the third generation and future wireless communication standards. This paper proposes several transmit diversity algorithms suitable for small wireless terminals and presents performance assessment in terms of average signal‐to‐noise ratio (SNR) and outage improvement, convergence, and complexity of operations. The algorithms presented herein are verified using data from measured indoor channels with variable antenna spacing and the results explained using measured radiation patterns for a two‐element array. It is shown that for a two‐element array, the best among the proposed techniques provides SNR improvement of about 3 dB in a tightly spaced array (inter‐element spacing of 0.1 wavelength at 2 GHz) typical of small wireless devices. Additionally, these techniques are shown to perform significantly better than a single antenna device in an indoor channel considering realistic values of latency and propagation errors. 相似文献
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