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Abstract We have been interested in the development of rubisco‐based biomimetic systems for reversible CO2capture from air. Our design of the chemical CO2capture and release (CCR) system is informed by the understanding of the binding of the activator CO2(ACO2) in rubisco (ribulose‐1,5‐bisphosphate carboxylase/oxygenase). The active site consists of the tetrapeptide sequence Lys‐Asp‐Asp‐Glu (or KDDE) and the Lys sidechain amine is responsible for the CO2capture reaction. We are studying the structural chemistry and the thermodynamics of CO2capture based on the tetrapeptide CH3CO−KDDE−NH2(“KDDE”) in aqueous solution to develop rubisco mimetic CCR systems. Here, we report the results of1H NMR and13C NMR analyses of CO2capture by butylamine and by KDDE. The carbamylation of butylamine was studied to develop the NMR method and with the protocol established, we were able to quantify the oligopeptide carbamylation at much lower concentration. We performed a pH profile in the multi equilibrium system and measured amine species and carbamic acid/carbamate species by the integration of1H NMR signals as a function of pH in the range 8≤pH≤11. The determination of ΔG1(R) for the reaction R−NH2+CO2R−NH−COOH requires the solution of a multi‐equilibrium equation system, which accounts for the dissociation constantsK2andK3controlling carbonate and bicarbonate concentrations, the acid dissociation constantK4of the conjugated acid of the amine, and the acid dissociation constantK5of the alkylcarbamic acid. We show how the multi‐equilibrium equation system can be solved with the measurements of the daughter/parent ratioX, the knowledge of the pH values, and the initial concentrations [HCO3−]0and [R‐NH2]0. For the reaction energies of the carbamylations of butylamine and KDDE, our best values are ΔG1(Bu)=−1.57 kcal/mol and ΔG1(KDDE)=−1.17 kcal/mol. Both CO2capture reactions are modestly exergonic and thereby ensure reversibility in an energy‐efficient manner. These results validate the hypothesis that KDDE‐type oligopeptides may serve as reversible CCR systems in aqueous solution and guide designs for their improvement.
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Apparent nitrous acid dissociation across environmentally relevant temperatures in freshwater and seawater
Abstract Nitrite is a ubiquitous compound found across aquatic systems and an intermediate in both the oxidative and reductive metabolisms transforming fixed nitrogen in the environment. Yet, the abiotic cycling of nitrite is often overlooked in favor of biologically mediated reactions. Here we quantify the apparent acid dissociation constant (pKa) between nitrous acid and its conjugate base nitrite in both freshwater and seawater systems across a range of environmentally relevant temperatures (5–35°C) using potentiometric‐based titration. In freshwater, we measured a pKa,NBSof 3.14 at 25°C and a pKa,Tof 2.87 for seawater at the same temperature. We quantify substantial effects of both salinity and temperature on the pKa, with colder and fresher water manifesting higher values and thus a greater proportion of protonated nitrite at any given pH. Because nitrous acid is unstable and decomposes to nitric oxide, the implications for the nitrous acid dissociation constant on ecosystem function are broad.
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- PAR ID:
- 10550393
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Limnology and Oceanography
- Volume:
- 69
- Issue:
- 12
- ISSN:
- 0024-3590
- Format(s):
- Medium: X Size: p. 2859-2866
- Size(s):
- p. 2859-2866
- Sponsoring Org:
- National Science Foundation
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