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The influence of the amine structure (secondary, tertiary, pyridinic) in amine-functionalized polymeric membranes on the mechanism of CO2 transport across the membrane is investigated in this work using operando surface enhanced Raman spectroscopy (SERS) and in-situ transmission FTIR spectroscopy. Specifically, the mechanism of CO2 transport across poly-N-methyl-N-vinylamine (PMVAm), poly-N, N-dimethyl-N-vinylamine (PDVAm), and poly(4-vinylpyridine) (P4VP) membranes was investigated by measuring CO2 permeances/selectivities of the membranes and simultaneously detecting CO2 transport intermediates (e.g., carbamate, bicarbonate) formed in the membrane under operating conditions using SERS and FTIR spectroscopy. While permeation measurements suggest that CO2 moves across all membranes via a facilitated transport mechanism, operando SERS and in-situ FTIR results suggest that the molecular-level details of the facilitated transport process are highly sensitive to the structure of the amine functional group. For membranes with secondary (PMVAm) and tertiary (PDVAm) amines, CO2 moves across the membrane as a mixture of both carbamate and bicarbonate species. For P4VP, which has pyridinic amine groups, no CO2-derived intermediates were detected suggesting a new facilitated transport mechanism involving weak interactions between CO2 and the pyridinic nitrogen group without transformation of CO2 into carbamate, bicarbonate, or other intermediate species. Such a facilitated transport mechanism has not been reported in the literature to our knowledge. 

Herein, we present a membrane-based system designed to capture CO2 from dilute mixtures and convert the captured CO2 into value-added products in a single, integrated process operated continuously at mild conditions. Specifically, we demonstrate that quaternized poly(4-vinylpyridine) (P4VP) membranes are selective CO2 separation membranes that are also catalytically active for cyclic carbonate synthesis from the cycloaddition of CO2 to epichlorohydrin. We further demonstrate that quaternized P4VP membranes can integrate CO2 capture, including from dilute mixtures down to 0.1 kPa CO2, with CO2 conversion to cyclic carbonates at 57 °C and atmospheric pressure. The catalytic membrane acts as both the CO2 capture and conversion medium, providing an energy-efficient alternative to sorbent-based capture, compression, transport, and storage. The membrane is also potentially tunable for CO2 conversion to a variety of products, including chemicals and fuels not limited to cyclic carbonates, which would be a transformative shift in carbon capture and utilization technology. 

Cholinergic signaling, i.e., neurotransmission mediated by acetylcholine, is involved in a host of physiological processes, including learning and memory. Cholinergic dysfunction is commonly associated with neurodegenerative diseases, including Alzheimer’s disease. In the gut, acetylcholine acts as an excitatory neuromuscular signaler to mediate smooth muscle contraction, which facilitates peristaltic propulsion. Gastrointestinal dysfunction has also been associated with Alzheimer’s disease. This research focuses on the preparation of an electrochemical enzyme-based biosensor to monitor cholinergic signaling in the gut and its application for measuring electrically stimulated acetylcholine release in the mouse colon ex vivo. The biosensors were prepared by platinizing Pt microelectrodes through potential cycling in a potassium hexachloroplatinate (IV) solution to roughen the electrode surface and improve adhesion of the multienzyme film. These electrodes were then modified with a permselective poly(m-phenylenediamine) polymer film, which blocks electroactive interferents from reaching the underlying substrate while remaining permeable to small molecules like H2O2. A multienzyme film containing choline oxidase and acetylcholinesterase was then drop-cast on these modified electrodes. The sensor responds to acetylcholine and choline through the enzymatic production of H2O2, which is electrochemically oxidized to produce an increase in current with increasing acetylcholine or choline concentration. Important figures of merit include a sensitivity of 190 ± 10 mA mol−1 L cm−2, a limit of detection of 0.8 μmol L−1, and a batch reproducibility of 6.1% relative standard deviation at room temperature. These sensors were used to detect electrically stimulated acetylcholine release from mouse myenteric ganglia in the presence and absence of tetrodotoxin and neostigmine, an acetylcholinesterase inhibitor. 

By influencing soil organic carbon (SOC), cover crops play a key role in shaping soil health and hence the system's long‐term sustainability. However, the magnitude by which cover crops impacts SOC depends on multiple factors, including soil type, climate, crop rotation, tillage type, cover crop growth, and years under management. To elucidate how these multiple factors influence the relative impact of cover crops on SOC, we conducted a meta‐analysis on the impacts of cover crops within rotations that included corn (Zea maysL.) on SOC accumulation. Information on climatic conditions, soil characteristics, management, and cover crop performance was extracted, resulting in 198 paired comparisons from 61 peer‐reviewed studies. Over the course of each study, cover crops on average increased SOC by 7.3% (95% CI, 4.9%–9.6%). Furthermore, the impact of cover crop–induced increases in percent change SOC was evaluated across soil textures, cover crop types, crop rotations, biomass amounts, cover crop durations, tillage practices, and climatic zones. Our results suggest that current cover crop–based corn production systems are sequestering 5.5 million Mg of SOC per year in the United States and have the potential to sequester 175 million Mg SOC per year globally. These findings can be used to improve carbon footprint calculations and develop science‐based policy recommendations. Taken altogether, cover cropping is a promising strategy to sequester atmospheric C and hence make corn production systems more resilient to changing climates.