NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems
Abstract Nuclear magnetic resonance (NMR) lineshape analysis is a powerful tool for the study of chemical kinetics. Here we provide techniques for analysis of the relationship between experimentally observed spin kinetics (transitions between different environments $$A,B,\dots$$ A , B , ⋯ ) and corr...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2022-10-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-022-20136-4 |
| _version_ | 1811250026191519744 |
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| author | Václav Březina Lenka Hanyková Nadiia Velychkivska Jonathan P. Hill Jan Labuta |
| author_facet | Václav Březina Lenka Hanyková Nadiia Velychkivska Jonathan P. Hill Jan Labuta |
| author_sort | Václav Březina |
| collection | DOAJ |
| description | Abstract Nuclear magnetic resonance (NMR) lineshape analysis is a powerful tool for the study of chemical kinetics. Here we provide techniques for analysis of the relationship between experimentally observed spin kinetics (transitions between different environments $$A,B,\dots$$ A , B , ⋯ ) and corresponding chemical kinetics (transitions between distinct chemical species; e.g., free host and complexed host molecule). The advantages of using analytical solutions for two-, three- or generally N-state exchange lineshapes (without J-coupling) over the widely used numerical calculation for NMR spectral fitting are presented. Several aspects of exchange kinetics including the generalization of coalescence conditions in two-state exchange, the possibility of multiple processes between two states, and differences between equilibrium and steady-state modes are discussed. ‘Reduced equivalent schemes’ are introduced for spin kinetics containing fast-exchanging states, effectively reducing the number of exchanging states. The theoretical results have been used to analyze a host–guest system containing an oxoporphyrinogen complexed with camphorsulfonic acid and several other literature examples, including isomerization, protein kinetics, or enzymatic reactions. The theoretical treatment and experimental examples present an expansion of the systematic approach to rigorous analyses of systems with rich chemical kinetics through NMR lineshape analysis. |
| first_indexed | 2024-04-12T15:57:53Z |
| format | Article |
| id | doaj.art-105b9b0a9a1e40d18be4d2ee15d9577c |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-04-12T15:57:53Z |
| publishDate | 2022-10-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-105b9b0a9a1e40d18be4d2ee15d9577c2022-12-22T03:26:18ZengNature PortfolioScientific Reports2045-23222022-10-0112111510.1038/s41598-022-20136-4NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systemsVáclav Březina0Lenka Hanyková1Nadiia Velychkivska2Jonathan P. Hill3Jan Labuta4International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)Faculty of Mathematics and Physics, Charles UniversityInternational Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)Abstract Nuclear magnetic resonance (NMR) lineshape analysis is a powerful tool for the study of chemical kinetics. Here we provide techniques for analysis of the relationship between experimentally observed spin kinetics (transitions between different environments $$A,B,\dots$$ A , B , ⋯ ) and corresponding chemical kinetics (transitions between distinct chemical species; e.g., free host and complexed host molecule). The advantages of using analytical solutions for two-, three- or generally N-state exchange lineshapes (without J-coupling) over the widely used numerical calculation for NMR spectral fitting are presented. Several aspects of exchange kinetics including the generalization of coalescence conditions in two-state exchange, the possibility of multiple processes between two states, and differences between equilibrium and steady-state modes are discussed. ‘Reduced equivalent schemes’ are introduced for spin kinetics containing fast-exchanging states, effectively reducing the number of exchanging states. The theoretical results have been used to analyze a host–guest system containing an oxoporphyrinogen complexed with camphorsulfonic acid and several other literature examples, including isomerization, protein kinetics, or enzymatic reactions. The theoretical treatment and experimental examples present an expansion of the systematic approach to rigorous analyses of systems with rich chemical kinetics through NMR lineshape analysis.https://doi.org/10.1038/s41598-022-20136-4 |
| spellingShingle | Václav Březina Lenka Hanyková Nadiia Velychkivska Jonathan P. Hill Jan Labuta NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems Scientific Reports |
| title | NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems |
| title_full | NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems |
| title_fullStr | NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems |
| title_full_unstemmed | NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems |
| title_short | NMR lineshape analysis using analytical solutions of multi-state chemical exchange with applications to kinetics of host–guest systems |
| title_sort | nmr lineshape analysis using analytical solutions of multi state chemical exchange with applications to kinetics of host guest systems |
| url | https://doi.org/10.1038/s41598-022-20136-4 |
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