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Controlling the structure and reactivity of the chain-end group is a central objective in modern polymer chemistry. Here, we introduce 3,6-anhydrogalactal as a single-addition monomer that enables efficient and versatile chain-end functionalization of metathesis polymers. Readily synthesized from biomass-derived galactal, 3,6-anhydrogalactal exhibits excellent single-addition reactivity, allowing precise chain-end modifications even when introduced simultaneously with the propagating monomer. Theoretical calculations provide mechanistic insights into the unique reactivities governing its single-addition behavior. Its broad functional group compatibility facilitates diverse applications, including block copolymer synthesis, polymer-polymer coupling, and bioconjugation, demonstrating significant potential for advancing polymer materials and bioconjugation strategies.more » « lessFree, publicly-accessible full text available May 21, 2026
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Free, publicly-accessible full text available December 11, 2025
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Free, publicly-accessible full text available November 1, 2025
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Abstract The Arctic–Boreal Zone is rapidly warming, impacting its large soil carbon stocks. Here we use a new compilation of terrestrial ecosystem CO2fluxes, geospatial datasets and random forest models to show that although the Arctic–Boreal Zone was overall an increasing terrestrial CO2sink from 2001 to 2020 (mean ± standard deviation in net ecosystem exchange, −548 ± 140 Tg C yr−1; trend, −14 Tg C yr−1;P < 0.001), more than 30% of the region was a net CO2source. Tundra regions may have already started to function on average as CO2sources, demonstrating a shift in carbon dynamics. When fire emissions are factored in, the increasing Arctic–Boreal Zone sink is no longer statistically significant (budget, −319 ± 140 Tg C yr−1; trend, −9 Tg C yr−1), and the permafrost region becomes CO2neutral (budget, −24 ± 123 Tg C yr−1; trend, −3 Tg C yr−1), underscoring the importance of fire in this region.more » « lessFree, publicly-accessible full text available February 1, 2026
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Abstract The absence of orthogonal aminoacyl-transfer RNA (tRNA) synthetases that accept non-l-α-amino acids is a primary bottleneck hindering the in vivo translation of sequence-defined hetero-oligomers and biomaterials. Here we report that pyrrolysyl-tRNA synthetase (PylRS) and certain PylRS variants accept α-hydroxy, α-thio andN-formyl-l-α-amino acids, as well as α-carboxy acid monomers that are precursors to polyketide natural products. These monomers are accommodated and accepted by the translation apparatus in vitro; those with reactive nucleophiles are incorporated into proteins in vivo. High-resolution structural analysis of the complex formed between one PylRS enzyme and am-substituted 2-benzylmalonic acid derivative revealed an active site that discriminates prochiral carboxylates and accommodates the large size and distinct electrostatics of an α-carboxy substituent. This work emphasizes the potential of PylRS-derived enzymes for acylating tRNA with monomers whose α-substituent diverges substantially from the α-amine of proteinogenic amino acids. These enzymes or derivatives thereof could synergize with natural or evolved ribosomes and/or translation factors to generate diverse sequence-defined non-protein heteropolymers.more » « less
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Abstract. Studies in recent decades have shown strong evidence of physical and biological changes in the Arctic tundra, largely in response to rapid rates of warming. Given the important implications of these changes for ecosystem services, hydrology, surface energy balance, carbon budgets, and climate feedbacks, research on the trends and patterns of these changes is becoming increasingly important and can help better constrain estimates of local, regional, and global impacts as well as inform mitigation and adaptation strategies. Despite this great need, scientific understanding of tundra ecology and change remains limited, largely due to the inaccessibility of this region and less intensive studies compared to other terrestrial biomes. A synthesis of existing datasets from past field studies can make field data more accessible and open up possibilities for collaborative research as well as for investigating and informing future studies. Here, we synthesize field datasets of vegetation and active-layer properties from the Alaskan tundra, one of the most well-studied tundra regions. Given the potentially increasing intensive fire regimes in the tundra, fire history and severity attributes have been added to data points where available. The resulting database is a resource that future investigators can employ to analyze spatial and temporal patterns in soil, vegetation, and fire disturbance-related environmental variables across the Alaskan tundra. This database, titled the Synthesized Alaskan Tundra Field Database (SATFiD), can be accessed at the Oak Ridge National Laboratory Distributed Active Archive Center (ORNL DAAC) for Biogeochemical Dynamics (Chen et al., 2023: https://doi.org/10.3334/ORNLDAAC/2177).more » « less