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1. NOAH-( ¹⁵ N/ ¹³ C)-CEST NMR supersequence for dynamics studies of biomolecules

   https://doi.org/10.1039/D2CC02015G  

   Cabrera Allpas, Rodrigo; Hansen, Alexandar L.; Brüschweiler, Rafael (August 2022, Chemical Communications)

   An NMR supersequence is introduced for the rapid acquisition of 15 N-CEST and methyl- 13 C-CEST experiments in the same pulse sequence for applications to proteins. The high sensitivity and accuracy allows the simultaneous quantitative characterization of backbone and side-chain dynamics on the millisecond timescale ideal for routine screening for alternative protein states. 

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2. Quantifying the effects of long-range 13C-13C dipolar coupling on measured relaxation rates in RNA

   https://doi.org/10.1007/s10858-021-00368-8  

   Olenginski, Lukasz T.; Dayie, Theodore K. (April 2021, Journal of Biomolecular NMR)

   Abstract Selective stable isotope labeling has transformed structural and dynamics analysis of RNA by NMR spectroscopy. These methods can remove¹³C-¹³C dipolar couplings that complicate¹³C relaxation analyses. While these phenomena are well documented for sites with adjacent¹³C nuclei (e.g. ribose C1′), less is known about so-called isolated sites (e.g. adenosine C2). To investigate and quantify the effects of long-range (> 2 Å)¹³C-¹³C dipolar interactions on RNA dynamics, we simulated adenosine C2 relaxation rates in uniformly [U-¹³C/¹⁵N]-ATP or selectively [2-¹³C]-ATP labeled RNAs. Our simulations predict non-negligible¹³C-¹³C dipolar contributions from adenosine C4, C5, and C6 to C2 longitudinal (R₁) relaxation rates in [U-¹³C/¹⁵N]-ATP labeled RNAs. Moreover, these contributions increase at higher magnetic fields and molecular weights to introduce discrepancies that exceed 50%. This will become increasingly important at GHz fields. Experimental R₁measurements in the 61 nucleotide human hepatitis B virus encapsidation signal ε RNA labeled with [U-¹³C/¹⁵N]-ATP or [2-¹³C]-ATP corroborate these simulations. Thus, in the absence of selectively labeled samples, long-range¹³C-¹³C dipolar contributions must be explicitly taken into account when interpreting adenosine C2 R₁rates in terms of motional models for large RNAs. 

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3. Controls on Stable Methane Isotope Values in Northern Peatlands and Potential Shifts in Values Under Permafrost Thaw Scenarios

   https://doi.org/10.1029/2023JG007837  

   Kuhn, McKenzie A; Varner, Ruth K; McCalley, Carmody K; Perryman, Clarice R; Aurela, Mika; Burke, Sophia A; Chanton, Jeffrey P; Crill, Patrick M; DelGreco, Jessica; Deng, Jia; et al (July 2024, Journal of Geophysical Research: Biogeosciences)

   Abstract Northern peatlands are a globally significant source of methane (CH₄), and emissions are projected to increase due to warming and permafrost loss. Understanding the microbial mechanisms behind patterns in CH₄production in peatlands will be key to predicting annual emissions changes, with stable carbon isotopes (δ¹³C‐CH₄) being a powerful tool for characterizing these drivers. Given that δ¹³C‐CH₄is used in top‐down atmospheric inversion models to partition sources, our ability to model CH₄production pathways and associated δ¹³C‐CH₄values is critical. We sought to characterize the role of environmental conditions, including hydrologic and vegetation patterns associated with permafrost thaw, on δ¹³C‐CH₄values from high‐latitude peatlands. We measured porewater and emitted CH₄stable isotopes, pH, and vegetation composition from five boreal‐Arctic peatlands. Porewater δ¹³C‐CH₄was strongly associated with peatland type, with δ¹³C enriched values obtained from more minerotrophic fens (−61.2 ± 9.1‰) compared to permafrost‐free bogs (−74.1 ± 9.4‰) and raised permafrost bogs (−81.6 ± 11.5‰). Variation in porewater δ¹³C‐CH₄was best explained by sedge cover, CH₄concentration, and the interactive effect of peatland type and pH (r² = 0.50,p < 0.001). Emitted δ¹³C‐CH₄varied greatly but was positively correlated with porewater δ¹³C‐CH₄. We calculated a mixed atmospheric δ¹³C‐CH₄value for northern peatlands of −65.3 ± 7‰ and show that this value is more sensitive to landscape drying than wetting under permafrost thaw scenarios. Our results suggest northern peatland δ¹³C‐CH₄values are likely to shift in the future which has important implications for source partitioning in atmospheric inversion models. 

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4. Revisiting Elevated δ ¹³ C Values of Sediment on Modern Carbonate Platforms

   https://doi.org/10.1029/2023GL107703  

   Trower, Elizabeth_J; Hibner, Brianna_M; Lincoln, Tyler_A; Dodd, Jacqueline_E; Hagen, Cedric_J; Cantine, Marjorie_D; Gomes, Maya_L (July 2024, Geophysical Research Letters)

   Abstract The measured carbon isotopic compositions of carbonate sediments (δ¹³C_carb) on modern platforms are commonly¹³C‐enriched compared to predicted values for minerals forming in isotopic equilibrium with the dissolved inorganic carbon (DIC) of modern seawater. This offset undermines the assumption that δ¹³C_carbvalues of analogous facies in the rock record are an accurate archive of information about Earth's global carbon cycle. We present a new data set of the diurnal variation in carbonate chemistry and seawater δ¹³C_DICvalues on a modern carbonate platform. These data demonstrate that δ¹³C_carbvalues on modern platforms are broadly representative of seawater, but only after accounting for the recent decrease in the δ¹³C value of atmospheric CO₂and shallow seawater DIC due to anthropogenic carbon release, a phenomenon commonly referred to as the¹³C Suess effect. These findings highlight an important, yet overlooked, aspect of some modern carbonate systems, which must inform their use as ancient analogs. 

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5. Carbon cycle dynamics and ecology revealed by the carbon isotopic composition of single organic microfossils during the Late Devonian Biotic Crisis

   https://doi.org/10.1111/gbi.12482  

   Cohen, Phoebe A.; Junium, Christopher K.; King Phillips, Ezekiel; Uveges, Benjamin T. (December 2021, Geobiology)

   Abstract We apply a new approach for the δ¹³C analysis of single organic‐walled microfossils (OWM) to three sites in the Appalachian Basin of New York (AB) that span the Late Devonian Biotic Crisis (LDBC). Our data provide new insights into the nature of the Frasnian–Famennian carbon cycle in the AB and also provide possible constraints on the paleoecology of enigmatic OWM ubiquitous in Paleozoic shale successions. The carbon isotope compositions of OWM are consistent with normal marine organic matter of autochthonous origins and range from −32 to −17‰, but average −25‰ across all samples and are consistently¹³C‐enriched compared to bulk sediments (δ¹³C_bulk) by ~0–10‰. We observe no difference between the δ¹³C_OWMof leiospheres (smooth‐walled) and acanthomorphic (spinose) acritarch OWM, indicating that our data are driven by ecological rather than taxonomic signals. We hypothesize that the offset between δ¹³C_OWMand δ¹³C_bulkis in part due to a large δ¹³C gradient in the AB water column where OWM utilized relatively¹³C‐enriched dissolved inorganic carbon near the surface. Thus, the organisms producing the balance of the total organic carbon were assimilating¹³C‐depleted C sources, including but not limited to respired organic carbon or byproducts of fermentation. We also observe a systematic decrease in both δ¹³C_OWMand δ¹³C_bulkof 3‰ from shoreward to open‐ocean facies that may reflect the effect of¹³C‐enriched dissolved inorganic carbon (DIC) derived from riverine sources in the relatively enclosed AB. The hypothesized steep carbon isotope gradient in the AB could be due to a strong biological pump; this in turn may have contributed to low oxygen bottom water conditions during the LDBC. This is the first time single‐microfossil δ¹³C_organalyses of eukaryotes have been directly compared to bulk δ¹³C_orgin the deep‐time fossil record. 

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