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1.
Giuseppe Spedalotto Dr. Robert Gericke Marta Lovisari Dr. Erik R. Farquhar Dr. Brendan Twamley Dr. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11983-11990
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII2 complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date. 相似文献
2.
In this paper we analyse some questions concerning trees on κ, both for the countable and the uncountable case, and the connections with Cohen reals. In particular, we provide a proof for one of the implications left open in [6, Question 5.2] about the diagram for regularity properties. 相似文献
3.
4.
Romain Tessier Raj Kumar Nandi Brendan G. Dwyer Daniel Abegg Charlotte Sornay Javier Ceballos Stphane Erb Sarah Cianfrani Alain Wagner Guilhem Chaubet Alexander Adibekian Jerome Waser 《Angewandte Chemie (International ed. in English)》2020,59(27):10961-10970
Current approaches to introduce terminal alkynes for bioorthogonal reactions into biomolecules still present limitations in terms of either reactivity, selectivity, or adduct stability. We present a method for the ethynylation of cysteine residues based on the use of ethynylbenziodoxolone (EBX) reagents. The acetylene group is directly introduced onto the thiol group of cysteine and can be used for copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) without further processing. Labeling proceeded with reaction rates comparable to or higher than the most often used iodoacetamide on peptides or maleimide on the antibody trastuzumab, and high cysteine selectivity was observed. The reagents were also used in living cells for cysteine proteomic profiling and displayed improved coverage of the cysteinome compared to previously reported iodoacetamide or hypervalent iodine reagents. Fine‐tuning of the EBX reagents allows optimization of their reactivity and physical properties. 相似文献
5.
Marcel Sickert Harald Weinstabl Brendan Peters Xiao Hou Mark Lautens 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(20):5247-5251
A palladium‐catalyzed intermolecular cross‐coupling of two aryl iodides is reported, giving polycyclic ring systems with a high level of convergence and efficiency. 相似文献
6.
Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance 下载免费PDF全文
Chris Knappy Daniela Barillà James Chong Dominic Hodgson Hugh Morgan Muhammad Suleman Christine Tan Peng Yao Brendan Keely 《Journal of mass spectrometry : JMS》2015,50(12):1420-1432
Higher homologues of widely reported C86 isoprenoid diglycerol tetraether lipid cores, containing 0–6 cyclopentyl rings, have been identified in (hyper)thermophilic archaea, representing up to 21% of total tetraether lipids in the cells. Liquid chromatography‐tandem mass spectrometry confirms that the additional carbon atoms in the C87‐88 homologues are located in the etherified chains. Structures identified include dialkyl and monoalkyl (‘H‐shaped’) tetraethers containing C40‐42 or C81‐82 hydrocarbons, respectively, many representing novel compounds. Gas chromatography‐mass spectrometric analysis of hydrocarbons released from the lipid cores by ether cleavage suggests that the C40 chains are biphytanes and the C41 chains 13‐methylbiphytanes. Multiple isomers, having different chain combinations, were recognised among the dialkyl lipids. Methylated tetraethers are produced by Methanothermobacter thermautotrophicus in varying proportions depending on growth conditions, suggesting that methylation may be an adaptive mechanism to regulate cellular function. The detection of methylated lipids in Pyrobaculum sp. AQ1.S2 and Sulfolobus acidocaldarius represents the first reported occurrences in Crenarchaeota. Soils and aquatic sediments from geographically distinct mesotemperate environments that were screened for homologues contained monomethylated tetraethers, with di‐ and trimethylated structures being detected occasionally. The structural diversity and range of occurrences of the C87‐89 tetraethers highlight their potential as complementary biomarkers for archaea in natural environments. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
7.
Benzylic Functionalization of Anthrones via the Asymmetric Ring Opening of Oxabicycles Utilizing a Fourth‐Generation Rhodium Catalytic System 下载免费PDF全文
Dr. Charles C. J. Loh Dr. Xiang Fang Brendan Peters Prof. Dr. Mark Lautens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13883-13887
While anthrones exist as privileged scaffolds in bioactive molecules, the enantioselective functionalization of anthrones is surprisingly scarce in the literature, with no asymmetric transition metal catalyzed example to date. Herein, we report the first asymmetric transition metal catalyzed benzylic functionalization of anthrones through the rhodium(I) catalyzed desymmetrization of oxabicycles. As previously developed rhodium(I) systems were found to be unsuitable for this substrate, a new robust fourth‐generation [Rh(cod)OH]2 based catalytic system was developed to address synthetic challenges in this protocol. 相似文献
8.
Inside Back Cover: Fragment‐Based Discovery of a Dual pan‐RET/VEGFR2 Kinase Inhibitor Optimized for Single‐Agent Polypharmacology (Angew. Chem. Int. Ed. 30/2015) 下载免费PDF全文
9.
Courtney Nagle Tyler Tracy Gregory Adams Daniel Scutella 《International Journal of Mathematical Education in Science & Technology》2017,48(4):573-586
This paper investigates outcomes of building students’ intuitive understanding of a limit as a function's predicted value by examining introductory calculus students’ conceptions of limit both before and after instruction. Students’ responses suggest that while this approach is successful at reducing the common limit equals function value misconception of a limit, new misconceptions emerged in students’ responses. Analysis of students’ reasoning indicates a lack of covariational reasoning that coordinates changes in both x and y may be at the root of the emerging limit reached near x = c misconception. These results suggest that although dynamic interpretations of limit may be intuitive for many students, care must be taken to foster a dynamic conception that is both useful at the introductory calculus level and is in line with the formal notion of limit learned in advanced mathematics. In light of the findings, suggestions for adapting the pedagogical approach used in this study are provided. 相似文献
10.
Brendan Dubsky 《代数通讯》2017,45(9):4084-4092
We prove Koszulity of certain linear path categories obtained from connected graphs with some infinite directed walk. These categories can be viewed as locally quadratic dual to preprojective algebras. 相似文献