Sulfur Analogs of the Core Formose Cycle: A Free Energy Map
Using computational methods, we examine if the presence of H<sub>2</sub>S can tame the unruly formose reaction by generating a free energy map of the reaction thermodynamics and kinetics of sulfur analogs within the core cycle. With mercaptoaldehyde as the linchpin C<sub>2</sub&...
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MDPI AG
2024-12-01
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| Series: | Life |
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| author | Jeremy Kua Maria T. Peña Samantha N. Cotter John Leca |
| author_facet | Jeremy Kua Maria T. Peña Samantha N. Cotter John Leca |
| author_sort | Jeremy Kua |
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| description | Using computational methods, we examine if the presence of H<sub>2</sub>S can tame the unruly formose reaction by generating a free energy map of the reaction thermodynamics and kinetics of sulfur analogs within the core cycle. With mercaptoaldehyde as the linchpin C<sub>2</sub> species, and feeding the cycle with CH<sub>2</sub>O, selected aldol additions and enolizations are kinetically more favorable. Thione formation is thermodynamically less favored compared to aldehydes and ketones, but all these species can be connected by enolization reactions. In some sulfur analogs, the retroaldol transformation of a C4 species back into linchpin species is thermodynamically favorable, and we have found one route incorporating where incorporating sulfur selects for a specific pathway over others. However, as CH<sub>2</sub>O diminishes, the aldol addition of larger species is less favorable for the sulfur analogs. Our results also suggest that competing Cannizzaro side reactions are kinetically less favored and thermodynamically disfavored when H<sub>2</sub>S is abundant. |
| format | Article |
| id | doaj-art-e2d83586962d4a1092bf3cb580255d79 |
| institution | Kabale University |
| issn | 2075-1729 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | MDPI AG |
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| series | Life |
| spelling | doaj-art-e2d83586962d4a1092bf3cb580255d792025-01-24T13:38:24ZengMDPI AGLife2075-17292024-12-01151110.3390/life15010001Sulfur Analogs of the Core Formose Cycle: A Free Energy MapJeremy Kua0Maria T. Peña1Samantha N. Cotter2John Leca3Department of Chemistry & Biochemistry, University of San Diego, San Diego, CA 92110, USADepartment of Chemistry & Biochemistry, University of San Diego, San Diego, CA 92110, USADepartment of Chemistry & Biochemistry, University of San Diego, San Diego, CA 92110, USADepartment of Chemistry & Biochemistry, University of San Diego, San Diego, CA 92110, USAUsing computational methods, we examine if the presence of H<sub>2</sub>S can tame the unruly formose reaction by generating a free energy map of the reaction thermodynamics and kinetics of sulfur analogs within the core cycle. With mercaptoaldehyde as the linchpin C<sub>2</sub> species, and feeding the cycle with CH<sub>2</sub>O, selected aldol additions and enolizations are kinetically more favorable. Thione formation is thermodynamically less favored compared to aldehydes and ketones, but all these species can be connected by enolization reactions. In some sulfur analogs, the retroaldol transformation of a C4 species back into linchpin species is thermodynamically favorable, and we have found one route incorporating where incorporating sulfur selects for a specific pathway over others. However, as CH<sub>2</sub>O diminishes, the aldol addition of larger species is less favorable for the sulfur analogs. Our results also suggest that competing Cannizzaro side reactions are kinetically less favored and thermodynamically disfavored when H<sub>2</sub>S is abundant.https://www.mdpi.com/2075-1729/15/1/1origins of lifethermodynamicskineticsprebiotic chemistryformose reactionsulfur |
| spellingShingle | Jeremy Kua Maria T. Peña Samantha N. Cotter John Leca Sulfur Analogs of the Core Formose Cycle: A Free Energy Map Life origins of life thermodynamics kinetics prebiotic chemistry formose reaction sulfur |
| title | Sulfur Analogs of the Core Formose Cycle: A Free Energy Map |
| title_full | Sulfur Analogs of the Core Formose Cycle: A Free Energy Map |
| title_fullStr | Sulfur Analogs of the Core Formose Cycle: A Free Energy Map |
| title_full_unstemmed | Sulfur Analogs of the Core Formose Cycle: A Free Energy Map |
| title_short | Sulfur Analogs of the Core Formose Cycle: A Free Energy Map |
| title_sort | sulfur analogs of the core formose cycle a free energy map |
| topic | origins of life thermodynamics kinetics prebiotic chemistry formose reaction sulfur |
| url | https://www.mdpi.com/2075-1729/15/1/1 |
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