Activation of robust bonds by carbonyl complexes of Mn, Fe and Co
Historic discoveries and recent advances in activation of strong C–H, C–F, and C–O bonds using carbonyl complexes of Mn, Fe, and Co are reviewed.
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Historic discoveries and recent advances in activation of strong C–H, C–F, and C–O bonds using carbonyl complexes of Mn, Fe, and Co are reviewed.
This study demonstrates that the stability of cyclingin situLi anodes depends on their depth of discharge (DOD). High DOD cycling results in unstable performance due to the accumulation of interfacial degradation at Li/LLZO interfaces.
Abstract Thioamides are natural post-translational modifications of the peptide backbone and can be introduced synthetically to probe protein folding or functionalize peptides for translational applications. In this work, we demonstrate that thioamide-containing peptides with C-terminal thioesters can be efficiently generated using Knorr pyrazole activation and used in subsequent native chemical ligation reactions to generate thioamide-containing proteins. We compare this method to acyl azide activation and find that both routes provide similar yields. We also investigate ultrasound-mediated desulfurization of the ligation site cysteine for potential advantages over chemical radical initiators. Scaling up our syntheses allows us to study thioamide perturbations to the β-sheet region of the B1 domain of protein G (GB1) as well as β-strand interactions in amyloid fibrils of the Parkinson’s disease protein α-synuclein. In both contexts, we observe dramatic destabilization of the β-sheet networks, manifested in decreased GB1 thermal stability and altered folding and slowed aggregation of α-synuclein. These findings illustrate the impact that a single atom substitution can have on cooperative hydrogen-bonding networks and prompt future study of both systems.
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Various methods of measuring the small thermally induced distortions experienced either by various points on the space vehicles or by deviations of surfaces from a known shape during solar thermal vacuum tests are examined. State-of-the-art application of both photographic and real time observation are discussed. The relative merits of each of the methods are compared and evaluated in their applications to different types of test articles and situations. Magnitudes of thermally induced distortions which may be expected to be routinely measurable by the various methods are presented and compared.
Zinc-silver oxide battery design for improved and activated charge retention, voltage control, and temperature stability
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The nature of connectivity between constituent atomic or molecular building blocks is fundamental in shaping the properties and functionality of materials. The extrapolation of emergent interatomic interactions to enable functional materials has driven transformative technological advancements. However, the bonding interactions used in material design have been largely static since the emergence of dynamic covalent chemistry ~30 years ago. Here we demonstrate that non-covalent chalcogen bonding (Ch-bonding) is a distinct mode of interatomic connectivity for constructing functional materials by design. This is established by leveraging self-complementary assembly of 1,2,5-telluradiazole moieties to construct a honeycomb-type permanently porous Ch-bonded organic framework, assembled and stabilized solely through non-covalent Te...N contacts. Empirical and computational studies of electronic structure, structural healing and lattice dynamics highlight the pi-type electronic communication, controlled assembly and modulated lattice dynamics in Trip3Tez-I arising directly from the unique nature of the Te...N Ch-bonding that holds substantial implications for next generation crystalline semiconductors. In addition to introducing a distinct class of permanently porous frameworks, this work establishes Ch-bonding as a programmable molecular tool for constructing functional materials with distinct properties.
A discussion is given of a containerless microgravity experiment aimed at measuring the interfacial tension of immiscible liquid pairs using a compound drop rotation method. The reasons for the failure to execute such experiments in microgravity are described. Also, the results of post-flight analyses used to confirm our arguments are presented.
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