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  1. We report the hyperfine-resolved rotational spectrum of the gas-phase phenoxy radical in the 8−25 GHz frequency range using cavity Fourier transform microwave spectroscopy. A complete assignment of its complex but well-resolved fine and hyperfine splittings yielded a precisely determined set of rotational constants, spin-rotation parameters, and nuclear hyperfine coupling constants. These results are interpreted with support from high-level quantum chemical calculations to gain detailed insight into the distribution of the unpaired π electron in this prototypical resonance-stabilized radical. The accurate laboratory rest frequencies enable studies of the chemistry of phenoxy in both the laboratory and space. The prospects of extending the present experimental and theoretical techniques to investigate the rotational spectra of isotopic variants and structural isomers of phenoxy and other important gas-phase radical intermediates that are yet undetected at radio wavelengths are discussed. 
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    Free, publicly-accessible full text available May 16, 2025
  2. We report the hyperfine-resolved rotational spectrum of gas-phase phenoxy radical in the 8–25 GHz frequency range using cavity Fourier transform microwave spectroscopy. A complete assignment of its complex but well-resolved fine and hyperfine splittings has yielded a precisely determined set of rotational constants, spin-rotation parameters, and nuclear hyperfine coupling constants. These results are interpreted with support from high-level quantum chemical calculations to gain detailed insight into the distribution of the unpaired π electron in this prototypical resonance-stabilized radical. The accurate laboratory rest frequencies enable studies of the chemistry of phenoxy in both the laboratory and in space. The prospects of extending the present experimental and theoretical techniques to investigate the rotational spectra of isotopic variants and structural isomers of phenoxy and other important gas-phase radical intermediates yet undetected at radio wavelengths are discussed. 
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    Free, publicly-accessible full text available January 17, 2025
  3. Abstract

    Recent detections of aromatic species in dark molecular clouds suggest that formation pathways may be efficient at very low temperatures and pressures, yet current astrochemical models are unable to account for their derived abundances, which can often deviate from model predictions by several orders of magnitude. The propargyl radical, a highly abundant species in the dark molecular cloud TMC-1, is an important aromatic precursor in combustion flames and possibly interstellar environments. We performed astrochemical modeling of TMC-1 using the three-phase gas-grain codeNAUTILUSand an updated chemical network, focused on refining the chemistry of the propargyl radical and related species. The abundance of the propargyl radical has been increased by half an order of magnitude compared to the previous GOTHAM network. This brings it closer in line with observations, but it remains underestimated by 2 orders of magnitude compared to its observed value. Predicted abundances for the chemically related C4H3N isomers within an order of magnitude of observed values corroborate the high efficiency of CN addition to closed-shell hydrocarbons under dark molecular cloud conditions. The results of our modeling provide insight into the chemical processes of the propargyl radical in dark molecular clouds and highlight the importance of resonance-stabilized radicals in polycyclic aromatic hydrocarbon formation.

     
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  4. Abstract Cell divisions are accurately positioned to generate cells of the correct size and shape. In plant cells, the new cell wall is built in the middle of the cell by vesicles trafficked along an antiparallel microtubule and a microfilament array called the phragmoplast. The phragmoplast expands toward a specific location at the cell cortex called the division site, but how it accurately reaches the division site is unclear. We observed microtubule arrays that accumulate at the cell cortex during the telophase transition in maize (Zea mays) leaf epidermal cells. Before the phragmoplast reaches the cell cortex, these cortical-telophase microtubules transiently interact with the division site. Increased microtubule plus end capture and pausing occur when microtubules contact the division site-localized protein TANGLED1 or other closely associated proteins. Microtubule capture and pausing align the cortical microtubules perpendicular to the division site during telophase. Once the phragmoplast reaches the cell cortex, cortical-telophase microtubules are incorporated into the phragmoplast primarily by parallel bundling. The addition of microtubules into the phragmoplast promotes fine-tuning of the positioning at the division site. Our hypothesis is that division site-localized proteins such as TANGLED1 organize cortical microtubules during telophase to mediate phragmoplast positioning at the final division plane. 
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  5. Abstract We report the detection of the lowest-energy conformer of E -1-cyano-1,3-butadiene ( E -1- C 4 H 5 CN ), a linear isomer of pyridine, using the fourth data reduction of the GBT Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) deep spectral survey toward TMC-1 with the 100 m Green Bank Telescope. We perform velocity stacking and matched-filter analyses using Markov chain Monte Carlo simulations and find evidence for the presence of this molecule at the 5.1 σ level. We derive a total column density of 3.8 − 0.9 + 1.0 × 10 10 cm −2 , which is predominantly found toward two of the four velocity components we observe toward TMC-1. We use this molecule as a proxy for constraining the gas-phase abundance of the apolar hydrocarbon 1,3-butadiene. Based on the three-phase astrochemical modeling code NAUTILUS and an expanded chemical network, our model underestimates the abundance of cyano-1,3-butadiene by a factor of 19, with a peak column density of 2.34 × 10 10 cm −2 for 1,3-butadiene. Compared to the modeling results obtained in previous GOTHAM analyses, the abundance of 1,3-butadiene is increased by about two orders of magnitude. Despite this increase, the modeled abundances of aromatic species do not appear to change and remain underestimated by one to four orders of magnitude. Meanwhile, the abundances of the five-membered ring molecules increase proportionally with 1,3-butadiene by two orders of magnitude. We discuss the implications for bottom-up formation routes to aromatic and polycyclic aromatic molecules. 
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  6. Abstract Using data from the Green Bank Telescope (GBT) Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) survey, we report the first astronomical detection of the C 10 H − anion. The astronomical observations also provided the necessary data to refine the spectroscopic parameters of C 10 H − . From the velocity stacked data and the matched filter response, C 10 H − is detected at >9 σ confidence level at a column density of 4.04 − 2.23 + 10.67 × 10 11 cm −2 . A dedicated search for the C 10 H radical was also conducted toward TMC-1. In this case, the stacked molecular emission of C 10 H was detected at a ∼3.2 σ confidence interval at a column density of 2.02 − 0.82 + 2.68 × 10 11 cm −2 . However, as the determined confidence level is currently <5 σ , we consider the identification of C 10 H as tentative. The full GOTHAM data set was also used to better characterize the physical parameters including column density, excitation temperature, line width, and source size for the C 4 H, C 6 H, and C 8 H radicals and their respective anions, and the measured column densities were compared to the predictions from a gas/grain chemical formation model and from a machine learning analysis. Given the measured values, the C 10 H − /C 10 H column density ratio is ∼ 2.0 − 1.6 + 5.9 —the highest value measured between an anion and neutral species to date. Such a high ratio is at odds with current theories for interstellar anion chemistry. For the radical species, both models can reproduce the measured abundances found from the survey; however, the machine learning analysis matches the detected anion abundances much better than the gas/grain chemical model, suggesting that the current understanding of the formation chemistry of molecular anions is still highly uncertain. 
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