Heterocyclic arynes, or hetarynes, have been studied for over 100 years. However, challenges associated with observing these reactive species, as well as developing synthetically useful methods for ...their generation and trapping, have limited their use. This review provides a brief historical perspective on the field of hetarynes, in addition to a discussion of pyridyne and indolyne methodologies. Moreover, this review highlights the use of pyridynes, indolynes, and related strained intermediates in natural product synthesis.
Metal-free ring-opening metathesis polymerization (ROMP) utilizes organic photoredox mediators as alternatives to traditional metal-based ROMP initiators to allow the preparation of polymers without ...residual metal contamination. Herein we report studies exploring the use of endo-dicyclopentadiene (DCPD), a common ROMP monomer, to form linear polyDCPD and copolymers with norbornene. Subsequent cross-linking of the linear polyDCPD using thiol–ene chemistry allows for a completely metal-free preparation of cross-linked polyDCPD. Furthermore, the examination of a number of structurally related monomers offers insights into mechanistic details of this polymerization and demonstrates new monomers that can be utilized for metal-free ROMP.
Heterocyclic arynes have long been targeted as potential tools for the synthesis of substituted heterocycles. Recent advances have led to an improved understanding of the factors that determine ...regioselectivity in reactions of these strained intermediates and, in turn, the aryne distortion model. This paper highlights the use of this predictive model to enable the use of heterocyclic arynes, such as indolynes and pyridynes, in chemical synthesis.
Scorpius X-1 (Sco X-1) and x-ray transient XTE J1751-305 are low-mass x-ray binaries (LMXBs) that may emit continuous gravitational waves detectable in the band of ground-based interferometric ...observatories. Neutron stars in LMXBs could reach a torque-balance steady-state equilibrium in which angular momentum addition from infalling matter from the binary companion is balanced by angular momentum loss, conceivably due to gravitational-wave emission. Torque balance predicts a scale for detectable gravitational-wave strain based on observed x-ray flux. This paper describes a search for Sco X-1 and XTE J1751-305 in LIGO science run 6 data using the TwoSpect algorithm, based on searching for orbital modulations in the frequency domain. While no detections are claimed, upper limits on continuous gravitational-wave emission from Sco X-1 are obtained, spanning gravitational-wave frequencies from 40 to 2040 Hz and projected semimajor axes from 0.90 to 1.98 light-seconds. These upper limits are injection validated, equal any previous set in initial LIGO data, and extend over a broader parameter range. At optimal strain sensitivity, achieved at 165 Hz, the 95% confidence level random-polarization upper limit on dimensionless strain h0 is approximately 1.8×10−24. The closest approach to the torque-balance limit, within a factor of 27, is also at 165 Hz. Upper limits are set in particular narrow frequency bands of interest for J1751-305. These are the first upper limits known to date on r-mode emission from this XTE source. The TwoSpect method will be used in upcoming searches of Advanced LIGO and Virgo data.
Cnidaria, the sister group to Bilateria, is a highly diverse group of animals in terms of morphology, lifecycles, ecology, and development. How this diversity originated and evolved is not well ...understood because phylogenetic relationships among major cnidarian lineages are unclear, and recent studies present contrasting phylogenetic hypotheses. Here, we use transcriptome data from 15 newly-sequenced species in combination with 26 publicly available genomes and transcriptomes to assess phylogenetic relationships among major cnidarian lineages. Phylogenetic analyses using different partition schemes and models of molecular evolution, as well as topology tests for alternative phylogenetic relationships, support the monophyly of Medusozoa, Anthozoa, Octocorallia, Hydrozoa, and a clade consisting of Staurozoa, Cubozoa, and Scyphozoa. Support for the monophyly of Hexacorallia is weak due to the equivocal position of Ceriantharia. Taken together, these results further resolve deep cnidarian relationships, largely support traditional phylogenetic views on relationships, and provide a historical framework for studying the evolutionary processes involved in one of the most ancient animal radiations.
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