C-C bond-forming reactions of ground-state aryl halides under reductive activation

Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves as an electron donor, and assists the initiation of the reactions, but in DMSO, it is not required. The outcomes are compared and contrasted with a recent photochemical study on similar substrates. A particular difference is the prevalence of hydride shuttle reactions under relatively mild thermal conditions

Fishery dynamics of the California market squid (Loligo opalescens), as measured by satellite remote sensing

Novel data on the spatial and temporal distribution of fishing effort and population abundance are presented for the market squid fishery (Loligo opalescens) in the Southern California Bight, 1992−2000. Fishing effort was measured by the detection of boat lights by the Defense Meteorological Satellite Program (DMSP) Operational Linescan System (OLS). Visual confirmation of fishing vessels by nocturnal aerial surveys indicated that lights detected by satellites are reliable indicators of fishing effort. Overall, fishing activity was concentrated off the following Channel Islands: Santa Rosa, Santa Cruz, Anacapa, and Santa Catalina. Fishing activity occurred at depths of 100 m or less. Landings, effort, and squid abundance (measured as landings per unit of effort, LPUE) markedly declined during the 1997−98 El Niño; landings and LPUE increased afterwards. Within a fishing season, the location of fishing activity shifted from the northern shores of Santa Rosa and Santa Cruz Islands in October, the typical starting date for squid fishing in the Bight, to the southern shores by March, the typical end of the squid season. Light detection by satellites offers a source of fine-scale spatial and temporal data on fishing effort for the market squid fishery off California, and these data can be integrated with environmental data and fishing logbook data in the development of a management plan

Overturning established chemoselectivities : selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors

The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates

Metabolomic and Transcriptomic Insights into How Cotton Fiber Transitions to Secondary Wall Synthesis, Represses Lignification, and Prolongs Elongation

The morphogenesis of single-celled cotton fiber includes extreme elongation and staged cell wall differentiation. Designing strategies for improving cotton fiber for textiles and other uses relies on uncovering the related regulatory mechanisms. In this research we compared the transcriptomes and metabolomes of two Gossypium genotypes, Gossypium barbadense cv Phytogen 800 and G. hirsutum cv Deltapine 90. When grown in parallel, the two types of fiber developed similarly except for prolonged fiber elongation in the G. barbadense cultivar. The data were collected from isolated fibers between 10 to 28 days post anthesis (DPA) representing: primary wall synthesis to support elongation; transitional cell wall remodeling; and secondary wall cellulose synthesis, which was accompanied by continuing elongation only in G. barbadense fiber. Results: Of 206 identified fiber metabolites, 205 were held in common between the two genotypes. Approximately 38,000 transcripts were expressed in the fiber of each genotype, and these were mapped to the reference set and interpreted by homology to known genes. The developmental changes in the transcriptomes and the metabolomes were compared within and across genotypes with several novel implications. Transitional cell wall remodeling is a distinct stable developmental stage lasting at least four days (18 to 21 DPA). Expression of selected cell wall related transcripts was similar between genotypes, but cellulose synthase gene expression patterns were more complex than expected. Lignification was transcriptionally repressed in both genotypes. Oxidative stress was lower in the fiber of G. barbadense cv Phytogen 800 as compared to G. hirsutum cv Deltapine 90. Correspondingly, the G. barbadense cultivar had enhanced capacity for management of reactive oxygen species during its prolonged elongation period, as indicated by a 138-fold increase in ascorbate concentration at 28 DPA. Conclusions: The parallel data on deep-sequencing transcriptomics and non-targeted metabolomics for two genotypes of single-celled cotton fiber showed that a discrete developmental stage of transitional cell wall remodeling occurs before secondary wall cellulose synthesis begins. The data showed how lignification can be transcriptionally repressed during secondary cell wall synthesis, and they implicated enhanced capacity to manage reactive oxygen species through the ascorbate-glutathione cycle as a positive contributor to fiber length.National Science Foundation grant 1025947Cellular and Molecular Biolog

The HETDEX Survey: Emission Line Exploration and Source Classification

The Hobby-Eberly Telescope Dark Energy Experiment (HETDEX) is an untargeted spectroscopic survey that aims to measure the expansion rate of the Universe at $z \sim 2.4$ to 1% precision for both $H(z)$ and $D_A(z)$. HETDEX is in the process of mapping in excess of one million Lyman Alpha emitting (LAE) galaxies and a similar number of lower-z galaxies as a tracer of the large-scale structure. The success of the measurement is predicated on the post-observation separation of galaxies with Ly$\alpha$ emission from the lower-$z$ interloping galaxies, primarily [OII], with low contamination and high recovery rates. The Emission Line eXplorer (ELiXer) is the principal classification tool for HETDEX, providing a tunable balance between contamination and completeness as dictated by science needs. By combining multiple selection criteria, ELiXer improves upon the 20 Angstrom rest-frame equivalent width cut commonly used to distinguish LAEs from lower-$z$ [OII] emitting galaxies. Despite a spectral resolving power, R $\sim800$, that cannot resolve the [OII] doublet, we demonstrate the ability to distinguish LAEs from foreground galaxies with 98.1% accuracy. We estimate a contamination rate of Ly$\alpha$ by [OII] of 1.2% and a Ly$\alpha$ recovery rate of 99.1% using the default ELiXer configuration. These rates meet the HETDEX science requirements.Comment: 38 pages, 11 figure

American Head and Neck Society Endocrine Section clinical consensus statement: North American quality statements and evidence‐based multidisciplinary workflow algorithms for the evaluation and management of thyroid nodules

BackgroundCare for patients with thyroid nodules is complex and multidisciplinary, and research demonstrates variation in care. The objective was to develop clinical guidelines and quality metrics to reduce unwarranted variation and improve quality.MethodsMultidisciplinary expert consensus and modified Delphi approach. Source documents were workflow algorithms from Kaiser Permanente Northern California and Cancer Care of Ontario based on the 2015 American Thyroid Association management guidelines for adult patients with thyroid nodules and differentiated thyroid cancer.ResultsA consensus‐based, unified preoperative, perioperative, and postoperative workflow was developed for North American use. Twenty‐one panelists achieved consensus on 16 statements about workflow‐embedded process and outcomes metrics addressing safety, access, appropriateness, efficiency, effectiveness, and patient centeredness of care.ConclusionA panel of Canadian and United States experts achieved consensus on workflows and quality metric statements to help reduce unwarranted variation in care, improving overall quality of care for patients diagnosed with thyroid nodules.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/148340/1/hed25526_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/148340/2/hed25526.pd

HETDEX Public Source Catalog 1 -- Stacking 50K Lyman Alpha Emitters

We describe the ensemble properties of the $1.9 < z < 3.5$ Lyman Alpha Emitters (LAEs) found in the HETDEX survey's first public data release, HETDEX Public Source Catalog 1 (Mentuch Cooper et al. 2023). Stacking the low-resolution ($R \sim$ 800) spectra greatly increases the signal-to-noise ratio, revealing spectral features otherwise hidden by noise, and we show that the stacked spectrum is representative of an average member of the set. The flux limited, Ly$\alpha$ signal-to-noise ratio restricted stack of 50K HETDEX LAEs shows the ensemble biweight ``average" $z \sim 2.6$ LAE to be a blue (UV continuum slope $\sim -2.4$ and E(B-V) $< 0.1$), moderately bright (M$_{\text{UV}} \sim -19.7$) star forming galaxy with strong Ly$\alpha$ emission (log $L_{Ly\alpha}$ $\sim$ 42.8 and $W_{\lambda}$(Ly$\alpha$) $\sim$ 114\AA), and potentially significant leakage of ionizing radiation. The restframe UV light is dominated by a young, metal poor stellar population with an average age 5-15 Myr and metallicity of 0.2-0.3 Z$_{\odot}$.Comment: 17 pages, 11 figures, 2 data files (ApJ Accepted

Ferrets develop fatal influenza after inhaling small particle aerosols of highly pathogenic avian influenza virus A/Vietnam/1203/2004 (H5N1)

<p>Abstract</p> <p>Background</p> <p>There is limited knowledge about the potential routes for H5N1 influenza virus transmission to and between humans, and it is not clear whether humans can be infected through inhalation of aerosolized H5N1 virus particles. Ferrets are often used as a animal model for humans in influenza pathogenicity and transmissibility studies. In this manuscript, a nose-only bioaerosol inhalation exposure system that was recently developed and validated was used in an inhalation exposure study of aerosolized A/Vietnam/1203/2004 (H5N1) virus in ferrets. The clinical spectrum of influenza resulting from exposure to A/Vietnam/1203/2004 (H5N1) through intranasal verses inhalation routes was analyzed.</p> <p>Results</p> <p>Ferrets were successfully infected through intranasal instillation or through inhalation of small particle aerosols with four different doses of <it>Influenza virus </it>A/Vietnam/1203/2004 (H5N1). The animals developed severe influenza encephalomyelitis following intranasal or inhalation exposure to 10¹, 10², 10³, or 10⁴infectious virus particles per ferret.</p> <p>Conclusions</p> <p>Aerosolized <it>Influenza virus </it>A/Vietnam/1203/2004 (H5N1) is highly infectious and lethal in ferrets. Clinical signs appeared earlier in animals infected through inhalation of aerosolized virus compared to those infected through intranasal instillation.</p