Jameson Brian, Knobbe Kari, Glaser Rainer
Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65401, United States.
J Org Chem. 2023 Aug 18;88(16):11534-11544. doi: 10.1021/acs.joc.3c00701. Epub 2023 Aug 2.
We are developing energy-efficient and reversible carbon capture and release (CCR) systems that mimic the Lys carbamylation reaction in the active site of ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO). The multiequilibria scenario ammonium ion amine ⇌ carbamic acid ⇌ carbamate requires the presence of both free amine and CO for carbamylation and is affected by the p(). Two fluorination strategies aimed at ammonium ion p depression and low pH carbamylation were analyzed with (2,2,2-trifluoroethyl)butylamine and 2,2-difluoropropylamine and compared to butylamine . The determination of and Δ of the carbamylation reactions requires the solution of multiequilibria systems of equations based on initial conditions, H NMR measurements of carbamylation yields over a wide pH range, and knowledge of - values. and describe carbonic acid acidity, and ammonium ion acidities were measured experimentally. We calibrated carbamic acid acidities based on the measured value of aminocarbamic acid using isodesmic reactions. The proton exchange reactions were evaluated with ab initio computations at the APFD/6-311+G* level in combination with continuum solvation models and explicit solvation. The utilities of - will be discussed as they pertain to the development of fluorine-modified RuBisCO-mimetic reversible CCR systems.
我们正在开发模仿核酮糖-1,5-二磷酸羧化酶加氧酶（RuBisCO）活性位点中赖氨酸氨甲酰化反应的节能且可逆的碳捕获与释放（CCR）系统。多平衡情况铵离子⇌胺⇌氨基甲酸⇌氨基甲酸盐需要同时存在游离胺和CO才能进行氨甲酰化，并且受p（）影响。用（2,2,2-三氟乙基）丁胺和2,2-二氟丙胺分析了旨在降低铵离子p值和进行低pH氨甲酰化的两种氟化策略，并与丁胺进行了比较。氨甲酰化反应的和Δ的测定需要基于初始条件求解多平衡方程组、在宽pH范围内对氨甲酰化产率进行1H NMR测量以及了解-值。和描述碳酸酸度，铵离子酸度通过实验测量。我们使用等键反应基于氨基氨基甲酸的测量值校准氨基甲酸酸度。质子交换反应在APFD/6-311+G*水平结合连续溶剂化模型和显式溶剂化进行从头算计算评估。将讨论-在氟改性RuBisCO模拟可逆CCR系统开发中的应用。
