Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects
Abstract Hydroxymethanesulfonate is a key organosulfate linked to severe fine-particle pollution in fog and clouds, yet its rapid formation mechanism at the air-water interface remains elusive. Here, using metadynamics-biased ab initio molecular dynamics simulations, high-level quantum chemical calc...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-06-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-59712-3 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1850137929250242560 |
|---|---|
| author | Jifan Li Weiqiang Tang Jiabao Zhu Jinrong Yang Xiao He |
| author_facet | Jifan Li Weiqiang Tang Jiabao Zhu Jinrong Yang Xiao He |
| author_sort | Jifan Li |
| collection | DOAJ |
| description | Abstract Hydroxymethanesulfonate is a key organosulfate linked to severe fine-particle pollution in fog and clouds, yet its rapid formation mechanism at the air-water interface remains elusive. Here, using metadynamics-biased ab initio molecular dynamics simulations, high-level quantum chemical calculations and reaction density functional theory, we reveal that synergistic enthalpy-entropy effects govern the nucleophilic addition between bisulfite and formaldehyde. Compared to the gaseous reaction, the aqueous reaction faces a ~5.0 kcal/mol water reorganization barrier, partly offset by polarization effects. Ab initio molecular dynamics simulations show hydrogen bonding networks facilitate proton transfer via the Grotthuss mechanism, reducing activation entropy by ~5.5 kcal/mol. At the interface, partial solvation and restricted formaldehyde motion lower the enthalpy and configurational entropy by ~1.0 and ~0.9 kcal/mol, respectively, alongside a 1.9 kcal/mol electric field effect. These combined effects enhance the interfacial reaction rate by two orders of magnitude, offering insights into heterogeneous chemistry and strategies for winter haze mitigation. |
| format | Article |
| id | doaj-art-b7290b24958447c889dc6f652eca08b6 |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-b7290b24958447c889dc6f652eca08b62025-08-20T02:30:42ZengNature PortfolioNature Communications2041-17232025-06-0116111710.1038/s41467-025-59712-3Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effectsJifan Li0Weiqiang Tang1Jiabao Zhu2Jinrong Yang3Xiao He4Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal UniversitySchool of Chemical Engineering, East China University of Science and TechnologyShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal UniversityShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal UniversityShanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal UniversityAbstract Hydroxymethanesulfonate is a key organosulfate linked to severe fine-particle pollution in fog and clouds, yet its rapid formation mechanism at the air-water interface remains elusive. Here, using metadynamics-biased ab initio molecular dynamics simulations, high-level quantum chemical calculations and reaction density functional theory, we reveal that synergistic enthalpy-entropy effects govern the nucleophilic addition between bisulfite and formaldehyde. Compared to the gaseous reaction, the aqueous reaction faces a ~5.0 kcal/mol water reorganization barrier, partly offset by polarization effects. Ab initio molecular dynamics simulations show hydrogen bonding networks facilitate proton transfer via the Grotthuss mechanism, reducing activation entropy by ~5.5 kcal/mol. At the interface, partial solvation and restricted formaldehyde motion lower the enthalpy and configurational entropy by ~1.0 and ~0.9 kcal/mol, respectively, alongside a 1.9 kcal/mol electric field effect. These combined effects enhance the interfacial reaction rate by two orders of magnitude, offering insights into heterogeneous chemistry and strategies for winter haze mitigation.https://doi.org/10.1038/s41467-025-59712-3 |
| spellingShingle | Jifan Li Weiqiang Tang Jiabao Zhu Jinrong Yang Xiao He Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects Nature Communications |
| title | Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects |
| title_full | Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects |
| title_fullStr | Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects |
| title_full_unstemmed | Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects |
| title_short | Hydroxymethanesulfonate formation accelerated at the air-water interface by synergistic enthalpy-entropy effects |
| title_sort | hydroxymethanesulfonate formation accelerated at the air water interface by synergistic enthalpy entropy effects |
| url | https://doi.org/10.1038/s41467-025-59712-3 |
| work_keys_str_mv | AT jifanli hydroxymethanesulfonateformationacceleratedattheairwaterinterfacebysynergisticenthalpyentropyeffects AT weiqiangtang hydroxymethanesulfonateformationacceleratedattheairwaterinterfacebysynergisticenthalpyentropyeffects AT jiabaozhu hydroxymethanesulfonateformationacceleratedattheairwaterinterfacebysynergisticenthalpyentropyeffects AT jinrongyang hydroxymethanesulfonateformationacceleratedattheairwaterinterfacebysynergisticenthalpyentropyeffects AT xiaohe hydroxymethanesulfonateformationacceleratedattheairwaterinterfacebysynergisticenthalpyentropyeffects |