The Phosphite Puzzle: Concentrations of Metal Phosphites and their reactions between Phosphonoacetic Acid

Disciplines

Biochemistry | Chemistry

Abstract (300 words maximum)

The phosphorylation of organic molecules on the early Earth for prebiotic chemistry is an open research question. Phosphate minerals have low solubility in aqueous solutions, suggesting they were likely not a major source of phosphorous in the environments where life emerged (i.e., Darwin’s “warm little pond”). Phosphites or HPO32- have much higher solubility and several formation routes are plausible under early Earth conditions. Therefore, our investigation focuses on the reactivity of phosphites paired with the most abundant metal cations on the early Earth (Ca, Mg, Fe (II) and Fe (III)). While these metal phosphites are not commercially available, they can be synthesized using a straightforward procedure in the laboratory. Our hypothesis is that these metal phosphites could be the phosphorus source of orgoanophosphates via an indirect, two-step process of phosphonylation followed by oxidation. To test this hypothesis, we have synthesized and characterized calcium phosphite, magnesium phosphite, iron (II) and iron (III) phosphite, using a variety of analytical techniques (e.g., P-NMR, FTIR, TGA, XRD) to determine key values (e.g., frequency and J-coupling constants of the P-H bond and the robustness of the metal phosphites to oxidation). Before performing quantitative reactivity experiments, we established the saturated concentration of each metal phosphite and our organophosphorus calibration standard, phosphonacetic acid, using ICP-OES. These concentrations will be correlated with P-NMR peak intensities under acidic, neutral and basic pH conditions. This will allow percent yields for the phosphonylation of small organic molecules (i.e., glycerol, 1-propanol, 2-propanol) and subsequently oxidation to organophosphates to be calculated. This research will contribute to understanding the potential role of metal phosphites in the prebiotic formation of biologically relevant organophosphate molecules, providing insight into the emergence of life on Earth.

Academic department under which the project should be listed

CSM - Chemistry and Biochemistry

Primary Investigator (PI) Name

Heather Abbott-Lyon

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The Phosphite Puzzle: Concentrations of Metal Phosphites and their reactions between Phosphonoacetic Acid

The phosphorylation of organic molecules on the early Earth for prebiotic chemistry is an open research question. Phosphate minerals have low solubility in aqueous solutions, suggesting they were likely not a major source of phosphorous in the environments where life emerged (i.e., Darwin’s “warm little pond”). Phosphites or HPO32- have much higher solubility and several formation routes are plausible under early Earth conditions. Therefore, our investigation focuses on the reactivity of phosphites paired with the most abundant metal cations on the early Earth (Ca, Mg, Fe (II) and Fe (III)). While these metal phosphites are not commercially available, they can be synthesized using a straightforward procedure in the laboratory. Our hypothesis is that these metal phosphites could be the phosphorus source of orgoanophosphates via an indirect, two-step process of phosphonylation followed by oxidation. To test this hypothesis, we have synthesized and characterized calcium phosphite, magnesium phosphite, iron (II) and iron (III) phosphite, using a variety of analytical techniques (e.g., P-NMR, FTIR, TGA, XRD) to determine key values (e.g., frequency and J-coupling constants of the P-H bond and the robustness of the metal phosphites to oxidation). Before performing quantitative reactivity experiments, we established the saturated concentration of each metal phosphite and our organophosphorus calibration standard, phosphonacetic acid, using ICP-OES. These concentrations will be correlated with P-NMR peak intensities under acidic, neutral and basic pH conditions. This will allow percent yields for the phosphonylation of small organic molecules (i.e., glycerol, 1-propanol, 2-propanol) and subsequently oxidation to organophosphates to be calculated. This research will contribute to understanding the potential role of metal phosphites in the prebiotic formation of biologically relevant organophosphate molecules, providing insight into the emergence of life on Earth.