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排序方式: 共有153条查询结果,搜索用时 15 毫秒
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Micah T. Nelp Vahe Bandarian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(36):10773-10775
The biosynthesis of nitriles is known to occur through specialized pathways involving multiple enzymes; however, in bacterial and archeal biosynthesis of 7‐deazapurines, a single enzyme, ToyM, catalyzes the conversion of the carboxylic acid containing 7‐carboxy‐7‐deazaguanine (CDG) into its corresponding nitrile, 7‐cyano‐7‐deazaguanine (preQ0). The mechanism of this unusual direct transformation was shown to proceed via the adenylation of CDG, which activates it to form the newly discovered amide intermediate 7‐amido‐7‐deazaguanine (ADG). This is subsequently dehydrated to form the nitrile in a process that consumes a second equivalent of ATP. The authentic amide intermediate is shown to be chemically and kinetically competent. The ability of ToyM to activate two different substrates, an acid and an amide, accounts for this unprecedented one‐enzyme catalysis of nitrile synthesis, and the differential rates of these two half reactions suggest that this catalytic ability is derived from an amide synthetase that gained a new function. 相似文献
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Micah Stohlmann 《School science and mathematics》2019,119(5):287-296
Of the four subjects in an integrated science, technology, engineering, and mathematics (STEM) approach, mathematics has not received enough focus. This could be in part because mathematics teachers may be apprehensive or unsure about how to implement integrated STEM education in their classrooms. There are benefits to integrated STEM in a mathematics classroom though, including increased motivation, interest, and achievement for students. This article discusses three methods that middle school mathematics teachers can utilize to integrate STEM subjects. By focusing on open‐ended problems through engineering design challenges, mathematical modeling, and mathematics integrated with technology middle school students are more likely to see mathematics as relevant and valuable. Important considerations are discussed as well as recent research with these approaches. 相似文献
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We study the long-range asymptotic behavior for an out-of-equilibrium, countable, one-dimensional system of Brownian particles interacting through their rank-dependent drifts. Focusing on the semi-infinite case, where only the leftmost particle gets a constant drift to the right, we derive and solve the corresponding one-sided Stefan (free-boundary) equations. Via this solution we explicitly determine the limiting particle-density profile as well as the asymptotic trajectory of the leftmost particle. While doing so we further establish stochastic domination and convergence to equilibrium results for the vector of relative spacings among the leading particles. © 2019 Wiley Periodicals, Inc. 相似文献
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Dr. James P. Dombrowski Dr. Micah S. Ziegler Dr. Neelay M. Phadke Erum Mansoor Dr. Daniel S. Levine Dr. Ryan J. Witzke Prof. Dr. Martin Head-Gordon Prof. Dr. Alexis T. Bell Prof. Dr. T. Don Tilley 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):307-315
Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu)3]4− and HOM[OSi(OtBu)3]3− (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu)3]3Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown-4 afforded charge-separated ion pairs composed of monomeric anions M[OSi(OtBu)3]4− with outer-sphere [([12]crown-4)2Li]+ cations, and hydroxides {HOM[OSi(OtBu)3]3} with pendant [([12]crown-4)Li]+ cations. These molecular models were characterized by single-crystal X-ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown-4)Li]{HOM[OSi(OtBu)3]3} complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin–Ponndorf–Verley (MPV) transfer hydrogenations with Al/Ga-doped silica catalysts. 相似文献
6.
CJ Lombardo MS Glaz ZE Ooi DA Vanden Bout A Dodabalapur 《Physical chemistry chemical physics : PCCP》2012,14(38):13199-13203
Scanning confocal photocurrent microscopy has been used to characterize carrier collection efficiency in lateral bulk heterojunction devices. By analyzing the photocurrent mappings within these devices, the lateral extents of the space charge regions has been measured and reported. Modulation via white light bias or increased voltage bias is also shown to increase the size of the space charge regions. 相似文献
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Kharel MK Pahari P Shepherd MD Tibrewal N Nybo SE Shaaban KA Rohr J 《Natural product reports》2012,29(2):264-325
Covering: 1997 to 2010. The angucycline group is the largest group of type II PKS-engineered natural products, rich in biological activities and chemical scaffolds. This stimulated synthetic creativity and biosynthetic inquisitiveness. The synthetic studies used five different strategies, involving Diels-Alder reactions, nucleophilic additions, electrophilic additions, transition-metal mediated cross-couplings and intramolecular cyclizations to generate the angucycline frames. Biosynthetic studies were particularly intriguing when unusual framework rearrangements by post-PKS tailoring oxidoreductases occurred, or when unusual glycosylation reactions were involved in decorating the benz[a]anthracene-derived cores. This review follows our previous reviews, which were published in 1992 and 1997, and covers new angucycline group antibiotics published between 1997 and 2010. However, in contrast to the previous reviews, the main focus of this article is on new synthetic approaches and biosynthetic investigations, most of which were published between 1997 and 2010, but go beyond, e.g. for some biosyntheses all the way back to the 1980s, to provide the necessary context of information. 相似文献
10.
Thiol-ene UV-curable coatings using vegetable oil macromonomers 总被引:1,自引:0,他引:1
Micah Black 《European Polymer Journal》2009,45(5):1433-81
Allyl, acrylate, and vinyl ether derivatives of castor oil were synthesized and blended with multifunctional thiols for evaluation as thiol-ene ultraviolet (UV) curable systems. The UV cured films were characterized and evaluated via ASTM tests, gel content, and dynamic mechanical analysis (DMA) as a function of time. Fourier transform infrared spectroscopy and DMA studies established that property advancement resulted from auto-oxidation, continued thiol-ene polymerization, or a combination of both mechanisms. 相似文献