Extended reduction of Mo2Cp2(μ-Cl)(μ-P t Bu2)(NO)2 (1) with Na(Hg) in acetonitrile (MeCN) at room temperature resulted in an unprecedented full cleavage of the CN bond of a coordinated MeCN ...molecule to yield the vinylidene derivative NaMo2Cp2(μ-P t Bu2)(μ-CCH2)(NO)2, which upon protonation with (NH4)PF6 gave the ethylidyne complex Mo2Cp2(μ-P t Bu2)(μ-CMe)(NO)2 Mo1–Mo2 = 2.9218(2) Å in a selective and reversible way. Controlled reduction of 1 at 273 K yielded instead, after protonation, the 30-electron acetamidinate complex Mo2Cp2(μ-P t Bu2)(μ-κN:κN′-HNCMeNH)(μ-NO)PF6 Mo1–Mo2 = 2.603(2) Å, in a process thought to stem from the paramagnetic MeCN-bridged intermediate Mo2Cp2(μ-P t Bu2)(μ-NCMe)(NO)2, followed by a complex sequence of elementary steps including cleavage of the NO bond of a nitrosyl ligand.
Oxidation by water with H2 liberation is highly desirable, as it can serve as an environmentally friendly way for the oxidation of organic compounds. Herein, we report the oxidation of alkenes with ...water as the oxidant by using a catalyst combination of a dearomatized acridine-based PNP-Ru complex and indium(III) triflate. Compared to traditional Wacker-type oxidation, this transformation avoids the use of added chemical oxidants and liberates hydrogen gas as the only byproduct.
Post-translational protein–protein conjugation produces bioconjugates that are unavailable via genetic fusion approaches. A method for preparing protein–protein conjugates using π-clamp-mediated ...cysteine arylation with pentafluorophenyl sulfonamide functional groups is described. Two computationally designed antibodies targeting the SARS-CoV-2 receptor binding domain were produced (K D = 146, 581 nM) with a π-clamp sequence near the C-terminus and dimerized using this method to provide a 10–60-fold increase in binding (K D = 8–15 nM). When two solvent-exposed cysteine residues were present on the second protein domain, the π-clamp cysteine residue was selectively modified over an Asp-Cys-Glu cysteine residue, allowing for subsequent small-molecule conjugation. With this strategy, we build molecule–protein–protein conjugates with complete chemical control over the sites of modification.
This article addresses the concept of "communication" in strategic communication, and proposes a new lens through which to view communication in order to deepen knowledge of strategic communication, ...as well as to significantly improve the alignment of strategic communication with the demands of today's strategy development process. Looking at modern strategy theory, this article focuses on communication theory as an ongoing process of meaning construction. It posits that communication is a process that is interactive by nature and participatory at all levels. This process is not necessarily two-way but omnidirectional diachronic, with an emphasis on the external and internal arenas of continuous meaning presentations, negotiations, and constructions. Strategic communication, therefore, needs to be conceptualized as an agile management process in which the focus is on feeding these arenas for strategy building and implementation, and on testing strategic decisions by presenting and negotiating these in a continuous loop.
RNA thermometers are noncoding RNA structures located in the 5′ untranslated regions (UTRs) of genes that regulate gene expression through temperature-dependent conformational changes. The fourU ...class of RNA thermometers contains a specific motif in which four consecutive uracil nucleotides are predicted to base pair with the Shine-Dalgarno (SD) sequence in a stem. We employed a bioinformatic search to discover a fourU RNA thermometer in the 5′-UTR of the blyA gene of the Bacillus subtilis phage SPβc2, a bacteriophage that infects B. subtilis 168. blyA encodes an autolysin enzyme, N-acetylmuramoyl-l-alanine amidase, which is involved in the lytic life cycle of the SPβ prophage. We have biochemically validated the predicted RNA thermometer in the 5′-UTR of the blyA gene. Our study suggests that RNA thermometers may play an underappreciated yet critical role in the lytic life cycle of bacteriophages.
Discourse Analysis in Adults With and Without Communication Disorders: A Resource for Clinicians and Researchers provides state-of-the-art information about discourse analysis with sections on Aging, ...Aphasia, Cognitive Communication Disorders, and Neurodegenerative Diseases. The three renowned editors are actively engaged in the area of discourse. Expert clinical researchers introduce and organize each section, and chapters are authored by leaders involved in discourse research worldwide.
The 1:1 reaction of the carbene-stabilized dithiolene zwitterion 1 with BH3·SMe2 gave the dithiolene-based hydroborane 2 and the doubly hydrogen-capped CAAC species 3 via hydride-coupled reverse ...electron transfer processes. The mechanism of this transformation was probed computationally using density functional theory. The subsequent 2:1 reaction of 2 with 1 resulted in 4 and 3, suggesting that 1 can mediate the B–H bond activation not only for BH3 but also for monohydroboranes. In the presence of BH3·SMe2, 2 was unexpectedly converted to the corresponding diborane(4) complex 5 through a dehydrocoupling reaction at an elevated temperature.
Amines and carboxylic acids are abundant synthetic building blocks that are classically united to form an amide bond. To access new pockets of chemical space, we are interested in the development of ...amine–acid coupling reactions that complement the amide coupling. In particular, the formation of carbon–carbon bonds by formal deamination and decarboxylation would be an impactful addition to the synthesis toolbox. Here, we report a formal cross-coupling of alkyl amines and aryl carboxylic acids to form C(sp3)–C(sp2) bonds following preactivation of the amine–acid building blocks as a pyridinium salt and N-acyl-glutarimide, respectively. Under nickel-catalyzed reductive cross-coupling conditions, a diversity of simple and complex substrates are united in good to excellent yield, and numerous pharmaceuticals are successfully diversified. High-throughput experimentation was leveraged in the development of the reaction and the discovery of performance-enhancing additives such as phthalimide, RuCl3, and GaCl3. Mechanistic investigations suggest phthalimide may play a role in stabilizing productive Ni complexes rather than being involved in oxidative addition of the N-acyl-imide and that RuCl3 supports the decarbonylation event, thereby improving reaction selectivity.
The novel nitrosyl-bridged complex W2Cp2(μ-P t Bu2)(μ-κ:η-NO)(CO)(NO)(BAr4) Ar = 3,5-C6H3(CF3)2 was prepared in a multistep procedure starting from the hydride W2Cp2(μ-H)(μ-P t Bu2)(CO)4 and ...involving the new complexes W2Cp2(μ-P t Bu2)(CO)4(BF4), W2Cp2(μ-P t Bu2)(CO)2(NO)2(BAr4), and W2(μ-κ:η5-C5H4)Cp(μ-P t Bu2)(CO)(NO)2 as intermediates, which follow from reactions with HBF4·OEt2, NO, and Me3NO·2H2O, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with N(PPh3)2Cl, with concomitant NO rearrangement into the terminal coordination mode, to give W2ClCp2(μ-P t Bu2)(CO)(NO)2, and underwent N–O and W–W bond cleavages upon the addition of CN t Bu to give the mononuclear phosphinoimido complex WCp(NP t Bu2)(CN t Bu)2(BAr4). Another N–O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex W2Cp2(N)(μ-O)(μ-OP t Bu2)(NO)(BAr4), likely resulting from a N–O bond cleavage step following decarbonylation.
This open access book introduces how to manage important tasks in industrial wireless networks. Important tasks must be completed on time and with guaranteed quality; that is the consensus reached by ...system designers and users. However, for too long, important tasks have often been given unnecessary urgency, and people intuitively believe that important tasks should be executed first so that their performance can be guaranteed. Actually, in most cases, their performance can be guaranteed even if they are executed later, and the “early” resources can be utilized for other, more urgent tasks. Therefore, confusing importance with urgency hinders the proper use of system resources. In 2007, mixed criticality was proposed to indicate that a system may contain tasks of various importance levels. Since then, system designers and users have distinguished between importance and urgency. In the industrial field, due to the harsh environment they operate in, industrial wireless networks’ quality of service (QoS) has always been a bottleneck restricting their applications. Therefore, this book introduces criticality to label important data, which is then allocated more transmission resources, ensuring that important data’s QoS requirements can be met to the extent possible. To help readers understand how to apply mixed-criticality data to industrial wireless networks, the content is divided into three parts. First, we introduce how to integrate the model of mixed-criticality data into industrial wireless networks. Second, we explain how to analyze the schedulability of mixed-criticality data under existing scheduling algorithms. Third, we present a range of novel scheduling algorithms for mixed-criticality data. If you want to improve the QoS of industrial wireless networks, this book is for you.
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