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51.
Yeonjin Ko Mark W. Ruszczycky Sei‐Hyun Choi Prof. Dr. Hung‐wen Liu 《Angewandte Chemie (International ed. in English)》2015,54(3):860-863
DesII is a radical S‐adenosylmethionine (SAM) enzyme that catalyzes the C4‐deamination of TDP‐4‐amino‐4,6‐dideoxyglucose through a C3 radical intermediate. However, if the C4 amino group is replaced with a hydroxy group (to give TDP‐quinovose), the hydroxy group at C3 is oxidized to a ketone with no C4‐dehydration. It is hypothesized that hyperconjugation between the C4 C? N/O bond and the partially filled p orbital at C3 of the radical intermediate modulates the degree to which elimination competes with dehydrogenation. To investigate this hypothesis, the reaction of DesII with the C4‐epimer of TDP‐quinovose (TDP‐fucose) was examined. The reaction primarily results in the formation of TDP‐6‐deoxygulose and likely regeneration of TDP‐fucose. The remainder of the substrate radical partitions roughly equally between C3‐dehydrogenation and C4‐dehydration. Thus, changing the stereochemistry at C4 permits a more balanced competition between elimination and dehydrogenation. 相似文献
52.
High Catalytic Activity of Nitrogen and Sulfur Co‐Doped Nanoporous Graphene in the Hydrogen Evolution Reaction 下载免费PDF全文
Dr. Yoshikazu Ito Weitao Cong Dr. Takeshi Fujita Prof. Zheng Tang Prof. Mingwei Chen 《Angewandte Chemie (International ed. in English)》2015,54(7):2131-2136
Chemical doping has been demonstrated to be an effective way to realize new functions of graphene as metal‐free catalyst in energy‐related electrochemical reactions. Although efficient catalysis for the oxygen reduction reaction (ORR) has been achieved with doped graphene, its performance in the hydrogen evolution reaction (HER) is rather poor. In this study we report that nitrogen and sulfur co‐doping leads to high catalytic activity of nanoporous graphene in HER at low operating potential, comparable to the best Pt‐free HER catalyst, 2D MoS2. The interplay between the chemical dopants and geometric lattice defects of the nanoporous graphene plays the fundamental role in the superior HER catalysis. 相似文献
53.
Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SC 下载免费PDF全文
Dr. Meng‐Qiang Zhao Morgane Sedran Zheng Ling Maria R. Lukatskaya Olha Mashtalir Michael Ghidiu Boris Dyatkin Darin J. Tallman Prof. Thierry Djenizian Prof. Michel W. Barsoum Prof. Yury Gogotsi 《Angewandte Chemie (International ed. in English)》2015,54(16):4810-4814
Herein we electrochemically and selectively extract Ti from the MAX phase Ti2SC to form carbon/sulfur (C/S) nanolaminates at room temperature. The products are composed of multi‐layers of C/S flakes, with predominantly amorphous and some graphene‐like structures. Covalent bonding between C and S is observed in the nanolaminates, which render the latter promising candidates as electrode materials for Li‐S batteries. We also show that it is possible to extract Ti from other MAX phases, such as Ti3AlC2 , Ti3SnC2 , and Ti2GeC, suggesting that electrochemical etching can be a powerful method to selectively extract the “M” elements from the MAX phases, to produce “AX” layered structures, that cannot be made otherwise. The latter hold promise for a variety of applications, such as energy storage, catalysis, etc. 相似文献
54.
Substrate‐Tuned Catalysis of the Radical S‐Adenosyl‐L‐Methionine Enzyme NosL Involved in Nosiheptide Biosynthesis 下载免费PDF全文
Xinjian Ji Dr. Yongzhen Li Prof. Dr. Wei Ding Prof. Dr. Qi Zhang 《Angewandte Chemie (International ed. in English)》2015,54(31):9021-9024
NosL is a radical S‐adenosyl‐L ‐methionine (SAM) enzyme that converts L ‐Trp to 3‐methyl‐2‐indolic acid, a key intermediate in the biosynthesis of a thiopeptide antibiotic nosiheptide. In this work we investigated NosL catalysis by using a series of Trp analogues as the molecular probes. Using a benzofuran substrate 2‐amino‐3‐(benzofuran‐3‐yl)propanoic acid (ABPA), we clearly demonstrated that the 5′‐deoxyadenosyl (dAdo) radical‐mediated hydrogen abstraction in NosL catalysis is not from the indole nitrogen but likely from the amino group of L ‐Trp. Unexpectedly, the major product of ABPA is a decarboxylated compound, indicating that NosL was transformed to a novel decarboxylase by an unnatural substrate. Furthermore, we showed that, for the first time to our knowledge, the dAdo radical‐mediated hydrogen abstraction can occur from an alcohol hydroxy group. Our study demonstrates the intriguing promiscuity of NosL catalysis and highlights the potential of engineering radical SAM enzymes for novel activities. 相似文献
55.
L. Cavaleri 《International Journal of Non》2006,41(9):1068-1083
A dynamic identification technique in the time domain for time invariant systems under random external forces is presented. This technique is based on the use of the class of restricted potential models (RPM), which are characterized by a non-linear stiffness and a special form of damping, that is a product of the input power spectral density (PSD) matrix and the velocity gradient of a non-linear function of the total mechanical energy. By applying stochastic differential calculus and by specific analytical manipulations, some algebraic equations, depending on the response statistics and on the mechanic parameters that characterize RPM, are obtained. These equations can be used for the dynamic identification of the above mechanic parameters once the response statistics of the system to be identified are evaluated. The proposed technique allows one to identify single-degree-of-freedom or multi-degrees-of-freedom systems in the case of unmeasurable input. Further, the probabilistic characteristics of the external forces can be completely estimated in terms of PSD matrix. 相似文献
56.
The dual conservation laws of elasticity are systematically re-examined by using both Noether's variational approach and Coleman–Noll–Gurtin's thermodynamics approach. These dual conservation laws can be interpreted as the dual configurational force, and therefore they provide the dual energy–momentum tensor. Some previously unknown and yet interesting results in elasticity theory have been discovered. As an example, we note the following duality condition between the configuration force (energy–momentum tensor) and the dual configuration force (dual energy–momentum tensor) ,
This and other results derived in this paper may lead to a better understanding of configurational mechanics and therefore of mechanics of defects. 相似文献
57.
This study focuses on a novel harmonic balance formulation, the high-dimensional harmonic balance method. To investigate a non-linearity in the damping term, the system chosen for study is the Van der Pol's oscillator. Both unforced and forced oscillators are analyzed. The results from the analysis are compared with those obtained from the classical harmonic balance and the time marching (Runge-Kutta) methods. 相似文献
58.
两个相邻建筑物周围风环境的数值模拟 总被引:9,自引:0,他引:9
高层建筑物及其群体周围所引起的风环境问题正日益受到人们的重视。本文用数值模拟方法对两幢串列布置高层建筑周围的流场进行了模拟,讨论了建筑物高度、间距比等因素对风环境特性的影响。为了与两个相邻建筑物的流场进行比较,本文同时计算了单个建筑物周围流动的分布情况。数值模拟结果对揭示高层建筑群区域内再生风载荷的形成机理提供了一定的分析方法,为城市规划和高层建筑住宅小区设计提供了一定的理论参考和依据。 相似文献
59.
In this paper we develop a simple micromechanical model of a prestressed polycrystalline aggregate, in which the texture-induced and stress-induced anisotropies of the aggregate are precisely defined; here the word texture always refers to the texture of the aggregate at the given prestressed configuration, not to that of a perhaps fictitious natural state of the aggregate. We use this model to derive, for a prestressed orthotropic aggregate of cubic crystallites, a birefringence formula which shows explicitly the effects of the orthotropic texture on the acoustoelastic coefficients. From this formula we observe that, generally speaking, we cannot separate the total birefringence into two distinct parts, one reflecting purely the influence of stress on the birefringence, and the other encompassing all the effects of texture. The same formula, on the other hand, provides for each material specific quantitative criteria under which the separation of stress-induced and texture-induced birefringence would become meaningful in an approximate sense. 相似文献
60.
Back contact–absorber interface modification by inserting carbon intermediate layer and conversion efficiency improvement in Cu2ZnSn(S,Se)4 solar cell 下载免费PDF全文
Fangqin Zeng Kaiwen Sun Li Gong Liangxing Jiang Fangyang Liu Yanqing Lai Jie Li 《固体物理学:研究快报》2015,9(12):687-691
Carbon layers have been employed as intermediate layers between Mo back contact and Cu2ZnSn(S1–xSex)4(CZTSSe) absorber film prepared by sol–gel and post‐selenization method. Carbon layers with appropriate thickness can significantly inhibit the formation of MoSe2 and voids at bottom region of the absorber, and therefore reduce the series resistance remarkably. The conversion efficiency can be boosted by the introducing of the carbon layer from 6.20% to 7.24% by enhancement in short current density, fill factor and open voltage in comparison to the reference sample without carbon layer. However, excess thickness of carbon layer will worse device performance due to the deteriorated absorber crystallinity. In addition, the time‐resolved photoluminescence analysis shows that inserting the carbon layer with suitable thickness does not introduce recombination and lower minority lifetime. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献