Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation
We are developing energy-efficient and reversible carbon capture and release (CCR) systems that mimic the Lys201 carbamylation reaction in the active site of ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO). The multiequilibria scenario ammonium ion Xa ⇌ amine Xb ⇌ carbamic acid Xc ⇌ carbam...
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ftmissouriunivst:oai:scholarsmine.mst.edu:chem_facwork-4647 2023-10-01T03:55:21+02:00 Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation Jameson, Brian Knobbe, Kari Glaser, Rainer 2023-01-01T08:00:00Z application/pdf https://scholarsmine.mst.edu/chem_facwork/3644 https://doi.org/10.1021/acs.joc.3c00701 https://scholarsmine.mst.edu/context/chem_facwork/article/4647/viewcontent/Nuclear_Magnetic_Resonance_Study_of_CO2_Capture_by_______.pdf unknown Scholars' Mine https://scholarsmine.mst.edu/chem_facwork/3644 doi:10.1021/acs.joc.3c00701 https://scholarsmine.mst.edu/context/chem_facwork/article/4647/viewcontent/Nuclear_Magnetic_Resonance_Study_of_CO2_Capture_by_______.pdf © 2023 American Chemical Society, All rights reserved. Chemistry Faculty Research & Creative Works Chemistry text 2023 ftmissouriunivst https://doi.org/10.1021/acs.joc.3c00701 2023-09-02T22:26:26Z We are developing energy-efficient and reversible carbon capture and release (CCR) systems that mimic the Lys201 carbamylation reaction in the active site of ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO). The multiequilibria scenario ammonium ion Xa ⇌ amine Xb ⇌ carbamic acid Xc ⇌ carbamate Xd requires the presence of both free amine and CO2 for carbamylation and is affected by the pKa(Xa). Two fluorination strategies aimed at ammonium ion pKa depression and low pH carbamylation were analyzed with (2,2,2-trifluoroethyl) butylamine 2b and 2,2-difluoropropylamine 3b and compared to butylamine 1b. The determination of K1 and ΔG1 of the carbamylation reactions requires the solution of multiequilibria systems of equations based on initial conditions, 1H NMR measurements of carbamylation yields over a wide pH range, and knowledge of K2-K5 values. K2 and K3 describe carbonic acid acidity, and ammonium ion acidities K4 were measured experimentally. We calibrated carbamic acid acidities K5 based on the measured value K6 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 1-3 will be discussed as they pertain to the development of fluorine-modified RuBisCO-mimetic reversible CCR systems. Text Carbonic acid Missouri University of Science and Technology (Missouri S&T): Scholars' Mine K5 ENVELOPE(24.794,24.794,67.805,67.805) The Journal of Organic Chemistry 88 16 11534 11544 |
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Missouri University of Science and Technology (Missouri S&T): Scholars' Mine |
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ftmissouriunivst |
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unknown |
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Chemistry |
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Chemistry Jameson, Brian Knobbe, Kari Glaser, Rainer Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation |
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Chemistry |
description |
We are developing energy-efficient and reversible carbon capture and release (CCR) systems that mimic the Lys201 carbamylation reaction in the active site of ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO). The multiequilibria scenario ammonium ion Xa ⇌ amine Xb ⇌ carbamic acid Xc ⇌ carbamate Xd requires the presence of both free amine and CO2 for carbamylation and is affected by the pKa(Xa). Two fluorination strategies aimed at ammonium ion pKa depression and low pH carbamylation were analyzed with (2,2,2-trifluoroethyl) butylamine 2b and 2,2-difluoropropylamine 3b and compared to butylamine 1b. The determination of K1 and ΔG1 of the carbamylation reactions requires the solution of multiequilibria systems of equations based on initial conditions, 1H NMR measurements of carbamylation yields over a wide pH range, and knowledge of K2-K5 values. K2 and K3 describe carbonic acid acidity, and ammonium ion acidities K4 were measured experimentally. We calibrated carbamic acid acidities K5 based on the measured value K6 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 1-3 will be discussed as they pertain to the development of fluorine-modified RuBisCO-mimetic reversible CCR systems. |
format |
Text |
author |
Jameson, Brian Knobbe, Kari Glaser, Rainer |
author_facet |
Jameson, Brian Knobbe, Kari Glaser, Rainer |
author_sort |
Jameson, Brian |
title |
Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation |
title_short |
Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation |
title_full |
Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation |
title_fullStr |
Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation |
title_full_unstemmed |
Nuclear Magnetic Resonance Study Of CO2 Capture By Fluoroalkylamines: Ammonium Ion PKa Depression Via Fluorine Modification And Thermochemistry Of Carbamylation |
title_sort |
nuclear magnetic resonance study of co2 capture by fluoroalkylamines: ammonium ion pka depression via fluorine modification and thermochemistry of carbamylation |
publisher |
Scholars' Mine |
publishDate |
2023 |
url |
https://scholarsmine.mst.edu/chem_facwork/3644 https://doi.org/10.1021/acs.joc.3c00701 https://scholarsmine.mst.edu/context/chem_facwork/article/4647/viewcontent/Nuclear_Magnetic_Resonance_Study_of_CO2_Capture_by_______.pdf |
long_lat |
ENVELOPE(24.794,24.794,67.805,67.805) |
geographic |
K5 |
geographic_facet |
K5 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Chemistry Faculty Research & Creative Works |
op_relation |
https://scholarsmine.mst.edu/chem_facwork/3644 doi:10.1021/acs.joc.3c00701 https://scholarsmine.mst.edu/context/chem_facwork/article/4647/viewcontent/Nuclear_Magnetic_Resonance_Study_of_CO2_Capture_by_______.pdf |
op_rights |
© 2023 American Chemical Society, All rights reserved. |
op_doi |
https://doi.org/10.1021/acs.joc.3c00701 |
container_title |
The Journal of Organic Chemistry |
container_volume |
88 |
container_issue |
16 |
container_start_page |
11534 |
op_container_end_page |
11544 |
_version_ |
1778523751978106880 |