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  1. Abstract

    A great diversity of crustacean zooplankton found in inland and coastal waters produce embryos that settle into bottom sediments to form an egg bank. Embryos from these banks can remain dormant for centuries, creating a reservoir of genetic diversity. A large body of literature describes the ecological and evolutionary importance of zooplankton egg banks. However, literature on the physiological traits behind dormancy in crustacean zooplankton are limited. Most data on the physiology of dormancy comes from research on one species of anostracan, the brine shrimp,Artemia franciscana. Anoxia-induced dormancy in this species is facilitated by a profound and reversible acidification of the intracellular space. This acidification is accompanied by a reversible depletion of adenosine triphosphate (ATP). The present study demonstrates that acidification of the intracellular space also occurs in concert with a depletion of nucleoside triphosphates (NTPs) in the Antarctic copepod,Boeckella poppei. LikeA. franciscana, the depletion of NTPs and acidification are rapidly reversed during aerobic recovery inB. poppei. These data provide the first comparative evidence that extreme dormancy under anoxia in crustacean zooplankton is associated with intracellular acidification and an ability to recover from the depletion of ATP.

     
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  2. NMR pulse sequences visualizing 1 J CC and n J CC bond connectivity via an intermediate state of 13 C– 13 C double-quantum coherence and 1 H detection are an indispensable tool to solve small-molecule structures at the natural abundance level of 13 C. A longstanding issue with these experiments set up to display 2D spectra with single-quantum frequencies is that in addition to the 1 H– 13 C– 13 C correlations of interest, appearance of HSQC-type artifacts can complicate analysis and obscure J CC connectivities. The origin of these artifacts is described and remedies for their suppression are introduced. They include refocusing of 1 J CH couplings prior to creation of 13 C– 13 C double-quantum coherence, which is known to enhance sensitivity by reducing loss into zero-quantum coherence for pairs of two protonated 13 C. 
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    Free, publicly-accessible full text available April 26, 2024
  3. Prediction of anisotropic NMR data directly from solute-medium interaction is of significant theoretical and practical interest, particularly for structure elucidation, configurational analysis and conformational studies of complex organic molecules and natural products. Current prediction methods require an explicit structural model of the alignment medium: a requirement either impossible or impractical on a scale necessary for small organic molecules. Here we formulate a comprehensive mathematical framework for a parametrization protocol that deconvolutes an arbitrary surface of the medium into several simple local landscapes that are distributed over the medium's surface by specific orientational order parameters. The shapes and order parameters of these local landscapes are determined via fitting that maximizes the congruence between experimentally determined anisotropic NMR measurables and their predicted counterparts, thus avoiding the need for an a priori knowledge of the global medium morphology. This method achieves substantial improvements in the accuracy of predicted anisotropic NMR values compared to current methods, as demonstrated herein with sixteen natural products. Furthermore, because this formalism extracts structural commonalities of the medium by combining anisotropic NMR data from different compounds, its robustness and accuracy are expected to improve as more experimental data become available for further re-optimization of fitting parameters. 
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  4. Abstract

    Carbon‐centered radicals stabilized by adjacent boron atoms are underexplored reaction intermediates in organic synthesis. This study reports the development of vinyl cyclopropyl diborons (VCPDBs) as a versatile source of previously unknown homoallylic α,α‐diboryl radicals via thiyl radical catalyzed diboron‐directed ring opening. These diboryl stabilized radicals underwent smooth [3+2] cycloaddition with a variety of olefins to provide diboryl cyclopentanes in good to excellent diastereoselectivity. In contrast to thetrans‐diastereoselectivity observed with most of the dicarbonyl activated VCPs, the cycloaddition of VCPDBs showed a remarkable preference for formation ofcis‐cyclopentane diastereomer which was confirmed by quantitative NOE and 2D NOESY studies. Thecis‐stereochemistry of cyclopentane products enabled a concise intramolecular Heck reaction approach to rare tricyclic cyclopentanoid framework containing the diboron group. The mild reaction conditions also allowed a one‐pot VCP ring‐opening, cycloaddition‐oxidation sequence to afford disubstituted cyclopentanones. Control experiments and DFT analysis of reaction mechanism support a radical mediated pathway and provide a rationale for the observed diastereoselectivity. To the authors’ knowledge, these are the first examples of the use of geminal diboryl group as an activator of VCP ring opening and cycloaddition reaction of α‐boryl radicals.

     
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  5. In this report, we revise the structure for a previously reported synthetic product proposed to be the 1 R ,2 S -cannabidiol epoxide and reassign it as cannabielsoin using anisotropic NMR and synthetic chemistry methods. These results provide a direct link to the first known biological target and function of cannabielsoin. 
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  6. Abstract We provide the first combined cosmological analysis of the South Pole Telescope (SPT) and Planck cluster catalogs. The aim is to provide an independent calibration for Planck scaling relations, exploiting the cosmological constraining power of the SPT-SZ cluster catalog and its dedicated weak lensing (WL) and X-ray follow-up observations. We build a new version of the Planck cluster likelihood. In the ν Λ CDM scenario, focusing on the mass slope and mass bias of Planck scaling relations, we find α SZ = 1.49 − 0.10 + 0.07 and 1 − b SZ = 0.69 − 0.14 + 0.07 , respectively. The results for the mass slope show a ∼4 σ departure from the self-similar evolution, α SZ ∼ 1.8. This shift is mainly driven by the matter density value preferred by SPT data, Ω m = 0.30 ± 0.03, lower than the one obtained by Planck data alone, Ω m = 0.37 − 0.06 + 0.02 . The mass bias constraints are consistent both with outcomes of hydrodynamical simulations and external WL calibrations, (1 − b ) ∼ 0.8, and with results required by the Planck cosmic microwave background cosmology, (1 − b ) ∼ 0.6. From this analysis, we obtain a new catalog of Planck cluster masses M 500 . We estimate the ratio between the published Planck M SZ masses and our derived masses M 500 , as a “measured mass bias,” 1 − b M . We analyze the mass, redshift, and detection noise dependence of 1 − b M , finding an increasing trend toward high redshift and low mass. These results mimic the effect of departure from self-similarity in cluster evolution, showing different dependencies for the low-mass, high-mass, low- z , and high- z regimes. 
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  7. Abstract

    Cannabicitran is an important cannabinoid natural product produced byCannabis sativaand is often found at surprisingly high levels (up to ~10%) in “purified” commercial cannabidiol (CBD) extract preparations. Despite the prevalence of this molecule in CBD oil and other cannabinoid‐related products, and the rapidly expanding interest in cannabinoids for treatment of a wide range of physiological conditions, only unassigned1H NMR data and partial unambiguous13C assignments have been published. Herein, we report the complete1H and13C NMR assignments of cannabicitran and comparatively evaluate the performance of several density functional theory (DFT) methods with varying levels of theory for the calculation of NMR chemical shifts.

     
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