NMR Study of CO₂ Capture by Butylamine and Oligopeptide KDDE in Aqueous Solution: Capture Efficiency and Gibbs Free Energy of the Capture Reaction as a Function of pH**

Abstract

We have been interested in the development of rubisco-based biomimetic systems for reversible CO 2 capture from air. Our design of the chemical CO 2 capture and release (CCR) system is informed by the understanding of the binding of the activator CO 2 ( A CO 2 ) 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 CO 2 capture reaction. We are studying the structural chemistry and the thermodynamics of CO 2 capture based on the tetrapeptide CH 3 COÀ KDDEÀ NH 2 ("KDDE") in aqueous solution to develop rubisco mimetic CCR systems. Here, we report the results of 1 H NMR and 13 C NMR analyses of CO 2 capture 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 of 1 H NMR signals as a function of pH in the range 8 � pH � 11. The determination of ΔG 1 (R) for the reaction RÀ NH 2 + CO 2 !RÀ NHÀ COOH requires the solution of a multi-equilibrium equation system, which accounts for the dissociation constants K 2 and K 3 controlling carbonate and bicarbonate concentrations, the acid dissociation constant K 4 of the conjugated acid of the amine, and the acid dissociation constant K 5 of the alkylcarbamic acid. We show how the multi-equilibrium equation system can be solved with the measurements of the daughter/parent ratio X, the knowledge of the pH values, and the initial concentrations [HCO 3 À ] 0 and [R-NH 2 ] 0 . For the reaction energies of the carbamylations of butylamine and KDDE, our best values are ΔG 1 (Bu) = À 1.57 kcal/mol and ΔG 1 (KDDE) = À 1.17 kcal/mol. Both CO 2 capture 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.

Nuclear Magnetic Resonance Study of CO2 Capture by Fluoroalkylamines: Ammonium Ion pKa Depression via Fluorine Modification and Thermochemistry of Carbamylation

“…The magnitude of this pH-dependent shift is largest for hydrogens in the proximity to the N atom, i.e., ε 2 , α 2 , and α 3 . This feature is also observed in the parent system 1 …”

“…formation as a function of pH for 1 (blue, left), a maximum carbamylation of 27.8% was observed at a pH of 10.28, [20][21][22] and this value provides our reference. Maximum carbamylation of 2 (middle, red) occurs at pH = 8.10 with a 13.7% capture efficiency and at pH = 9.03 for 3 (right, green) with 60.9% capture efficiency.…”

“…The ΔG 1 (1) = −1.57 kcal/mol value [20][21][22] for the carbamylation of butylamine 1 falls between the respective value of the fluorinated amines ΔG 1 (3) < ΔG 1 (1) < ΔG 1 (2). The utility of each fluorine modification depends on ΔG 1 , the yield of carbamylation quantified by the carbamate mol fraction Y(3) > Y(1) > Y(2), and the pH at which maximum carbamylation occurs.…”

“…This feature is also observed in the parent system 1. 22 In contrast, the chemical shifts of the daughter signals dε 2 of 2 and dα 3 and dγ 3 of 3 are essentially constant over the entire pH range. The acid dissociation equilibrium carbamic acid Xc ⇌ carbamate Xd and the equilibrium carbamate Xd ⇌ zwitterion Xe both lie predominantly on the side of the carbamate (vide infra).…”

“…1 H NMR spectra were acquired for ammonium ions 2a and 3a (Figure 2), and they are compared to those of butylammonium ion 1a. 22 The peak labels describe the position relative to the N-atom (i.e., α, β, etc. ), and the subscript denotes the corresponding ammonium ion (2,2,2-trifluoro-ethyl)butylamine, 2, or 2,2-difluoropropylamine, 3.…”