Velazquezhopper1546

This Review describes the development of strategies for carbonyl-olefin metathesis reactions relying on stepwise, stoichiometric, or catalytic approaches. A comprehensive overview of currently available methods is provided starting with Paternò-Büchi cycloadditions between carbonyls and alkenes, followed by fragmentation of the resulting oxetanes, metal alkylidene-mediated strategies, [3 + 2]-cycloaddition approaches with strained hydrazines as organocatalysts, Lewis acid-mediated and Lewis acid-catalyzed strategies relying on the formation of intermediate oxetanes, and protocols based on initial carbon-carbon bond formation between carbonyls and alkenes and subsequent Grob-fragmentations. The Review concludes with an overview of applications of these currently available methods for carbonyl-olefin metathesis in complex molecule synthesis. Over the past eight years, the field of carbonyl-olefin metathesis has grown significantly and expanded from stoichiometric reaction protocols to efficient catalytic strategies for ring-closing, ring-opening, and cross carbonyl-olefin metathesis. The aim of this Review is to capture the status quo of the field and is expected to contribute to further advancements in carbonyl-olefin metathesis in the coming years.The presence of surface/deep defects in 4d- and 5d-perovskite oxide (ABO3, B = Nb, Ta, Mo, etc.) nanoparticles (NPs), originating from multivalent B-site cations, contributes to suppressing their metallic properties. These defect states can be removed using a H2/Ar thermal treatment, enabling the recovery of their electronic properties (i.e., low electrical resistivity, high carrier concentration, etc.) as expected from their electronic structure. Therefore, to engineer the electronic properties of these metastable perovskites, an oxygen-controlled crystallization approach coupled with a subsequent H2/Ar treatment was utilized. A comprehensive study of the effect of the post-treatment time on the electronic properties of these perovskite NPs was performed using a combination of scattering, spectroscopic, and computational techniques. These measurements revealed that a metallic-like state is stabilized in these oxygen-reduced NPs due to the suppression of deep rather than surface defects. Ultimately, this synthetic approach can be employed to synthesize ABO3 perovskite NPs with tunable electronic properties for application into electrochemical devices.Previous studies have characterized spatial patterns of pollution with land use regression (LUR) models from distributed passive or filter samplers at low temporal resolution. Large-scale deployment of low-cost sensors (LCS), which typically sample in real time, may enable time-resolved or real-time modeling of concentration surfaces. The aim of this study was to develop spatiotemporal models of PM2.5, NO2, and CO using an LCS network in Pittsburgh, Pennsylvania. We modeled daily average concentrations in August 2016-December 2017 across 50 sites. Land use variables included 13 time-independent (e.g., elevation) and time-dependent (e.g., temperature) predictors. We examined two models LUR and a machine-learning-enabled land use model (land use random forest, LURF). E-7386 solubility dmso The LURF models outperformed LUR models, with increase in the average externally cross-validated R2 of 0.10-0.19. Using wavelet decomposition to separate short-lived events from the regional background, we also created time-decomposed LUR and LURF models. Compared to the standard model, this resulted in improvement in R2 of up to 0.14. The time-decomposed models were more influenced by spatial parameters. Mapping our models across Allegheny County, we observed that time-decomposed LURF models created robust PM2.5 predictions, suggesting that this approach may improve our ability to map air pollutants at high spatiotemporal resolution.Cationic surfactants have a strong affinity to sorb to phospholipid membranes and thus possess an inherent potential to bioaccumulate, but there are few measurements of bioconcentration in fish. We measured the bioconcentration of 10 alkylamines plus two quaternary ammonium compounds in juvenile rainbow trout at pH 7.6, and repeated the measurements at pH 6.2 for 6 of these surfactants. The BCF of the amines with chain lengths ≤ C14 was positively correlated with chain length, increasing ∼0.5 log units per carbon. Their BCF was also pH dependent and approximately proportional to the neutral fraction of the amine in the water. The BCFs of the quaternary ammonium compounds showed no pH dependence and were >2 orders of magnitude less than for amines of the same chain length at pH 7.6. This indicates that systemic uptake of permanently charged cationic surfactants is limited. The behavior of the quaternary ammonium compounds and the two C16 amines studied was consistent with previous observations that these surfactants accumulate primarily to the gills and external surfaces of the fish. At pH 7.6 the BCF exceeded 2000 L kg-1 for 4 amines with chains ≥ C13, showing that bioconcentration can be considerable for some longer chained cationic surfactants.A platform, based on targeted integration of transgenes using recombinase-mediated cassette exchange (RMCE) coupled with CRISPR/Cas9, is increasingly being used for the development of mammalian cell lines that produce therapeutic proteins, because of reduced clonal variation and predictable transgene expression. However, low efficiency of the RMCE process has hampered its application in multicopy or multisite integration of transgenes. To improve RMCE efficiency, nuclear transport of RMCE components such as site-specific recombinase and donor plasmid was accelerated by incorporation of nuclear localization signal and DNA nuclear-targeting sequence, respectively. Consequently, the efficiency of RMCE in dual-landing pad human embryonic kidney 293 (HEK293) cell lines harboring identical or orthogonal pairs of recombination sites at two well-known human safe harbors (AAVS1 and ROSA26 loci), increased 6.7- and 8.1-fold, respectively. This platform with enhanced RMCE efficiency enabled simultaneous integration of transgenes at the two sites using a single transfection without performing selection and enrichment processes.