Stereochemical Differences in Fluorocyclopropyl Amides Enable Tuning of Btk Inhibition and Off-Target Activity
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The large amount of waste generated from polyethylene terephthalate (PET) packaging materials that have reached the end of life is creating a waste management issue that cannot be handled by mechanical recycling alone. Thus, it is imperative that alternate routes to recover and reuse these materials be pursued. A chemical recycling approach of mixed PET was demonstrated here that provides a mechanism by which PET waste can be efficiently recovered and repurposed to value-added products. The approach utilizes aminolysis of PET with a variety of amine nucleophiles, generating a small library of phthalimides with unique structures. In order to probe the high value of these products, the phthalimides were added to road-grade asphalt binder at 5 wt% and the resulting composite was evaluated. Specifically, rutting and fatigue characteristics as well as thermomechanical and creep performance were characterized and found to be improved by the inclusion of these additives by as much as 18%. In this work, additives made from deconstructed PET wastes were shown to improve the performance properties of asphalt at a variety of environmental conditions. These improvements would reduce the cost of road maintenance and provide a high-value market for waste PET. It is important to note that the asphalt binder utilized in this work was a commercial product already optimized for road conditions, not the raw bitumen; perhaps higher performance metrics could be obtained with virgin bitumen.
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While preparing a follow-up manuscript, we found an error in one of the orbital reduction factors used in our crystal field models, given in Scheme 2. The third equation in that scheme was published as ka2t2 = 1 - 12 N2 2 a'p ; however, the correct formula is k a2t2 = 1 - 12 N'a'p2. (Table Presented).
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If renewable energy resources continue to become a larger part of the generation mix in the United States (U.S.), so does the potential impact of prolonged periods of low wind and solar generation, known as variable renewable energy (VRE) droughts. In such a future, naturally occurring VRE droughts need to be evaluated for their potential impact on grid reliability. This study is the first of its kind to examine the impacts of compound VRE energy droughts in the Western U.S. across a range of potential future climate and infrastructure scenarios. We find that compound VRE drought severity may increase significantly in the future, primarily due to the dramatic increase in wind and solar generation needed in some future infrastructure scenarios. We find that in our future climate scenario, the variability of energy drought severity increases, which has implications for sizing energy storage necessary for mitigating drought events. We also examine the spatial patterns of compound VRE drought events that effect multiple regions of the grid simultaneously. These co-occurring events have distinct spatial patterns depending on the season. We observed overall fewer connected events in the future with the combined effect of potential climate and infrastructure changes, although in the fall we observe a climate-induced shift toward events which impact more regions simultaneously.
The synthesis and full characterization, including Nuclear Magnetic Resonance (NMR) data ( 1 H, 13 C{ 1 H} and 119 Sn{ 1 H}), for a series of Me 3 SnX (X = O-2,6-tBu 2 C 6 H 3 (1), (Me 3 Sn)N(2,6- i Pr 2 C 6 H 3 ) (3), NH-2,4,6- t Bu 3 C 6 H 2 (4), N(SiMe 3 ) 2 (5), NEt 2 , C 5 Me 5 (6), Cl, Br, I, and SnMe 3 ) compounds in benzene-d 6 , toluene-d 8 , dichloromethane-d 2 , chloroform-d 1 , acetonitrile-d 3 , and tetrahydrofuran-d 8 are reported. The X-ray crystal structures of Me 3 Sn(O-2,6- t Bu 2 C 6 H 3 ) (1), Me 3 Sn(O-2,6- i Pr 2 C 6 H 3 ) (2), and (Me 3 Sn)(NH-2,4,6- t Bu 3 C 6 H 2 ) (4) are also presented. As a result, these compiled data complement existing literature data and ease the characterization of these compounds by routine NMR experiments.
A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2 ) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.
The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input.
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