Was ferrocyanide a prebiotic reagent?

Keefe, Anthony D.; Miller, Stanley L.

doi:10.1007/bf01809851

Cited by 71 publications

(66 citation statements)

References 29 publications

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“…Experimentally, sulphide addition causes precipitation of FeS and NiS, and this is probably prebiotically relevant as it is thought that significant H 2 S was available from volcanic emissions. Alternatively-or additionally-it is possible that hydrogen cyanide could sequester the ferrous iron as hexacyanoferrate(II) [24]. This is an attractive possibility as it would both liberate phosphate and concentrate hydrogen cyanide; subsequent irradiation could then release the hydrogen cyanide [24].…”

Section: A Linked Source Of Phosphate and Lipids: Towards A Higher Ormentioning

confidence: 99%

Prebiotic chemistry: a new modus operandi

Powner

Sutherland

2011

Phil. Trans. R. Soc. B

120

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A variety of macromolecules and small molecules-(oligo)nucleotides, proteins, lipids and metabolites-are collectively considered essential to early life. However, previous schemes for the origin of life-e.g. the 'RNA world' hypothesis-have tended to assume the initial emergence of life based on one such molecular class followed by the sequential addition of the others, rather than the emergence of life based on a mixture of all the classes of molecules. This view is in part due to the perceived implausibility of multi-component reaction chemistry producing such a mixture. The concept of systems chemistry challenges such preconceptions by suggesting the possibility of molecular synergism in complex mixtures. If a systems chemistry method to make mixtures of all the classes of molecules considered essential for early life were to be discovered, the significant conceptual difficulties associated with pure RNA, protein, lipid or metabolism 'worlds' would be alleviated. Knowledge of the geochemical conditions conducive to the chemical origins of life is crucial, but cannot be inferred from a planetary sciences approach alone. Instead, insights from the organic reactivity of analytically accessible chemical subsystems can inform the search for the relevant geochemical conditions. If the common set of conditions under which these subsystems work productively, and compatibly, matches plausible geochemistry, an origins of life scenario can be inferred. Using chemical clues from multiple subsystems in this way is akin to triangulation, and constitutes a novel approach to discover the circumstances surrounding the transition from chemistry to biology. Here, we exemplify this strategy by finding common conditions under which chemical subsystems generate nucleotides and lipids in a compatible and potentially synergistic way. The conditions hint at a post-meteoritic impact origin of life scenario.

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Section: A Linked Source Of Phosphate and Lipids: Towards A Higher Ormentioning

confidence: 99%

Prebiotic chemistry: a new modus operandi

Powner

Sutherland

2011

Phil. Trans. R. Soc. B

120

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“…Another route for the concentration of cyanide was proposed by Arrhenius et al [6] 4 À ) has been mentioned as a possible abundant component of the primitive ocean [8], and ferrocyanides and ferricyanides have been suggested as compounds of prebiotic interest [9]. In a recent work, we demonstrated that Prussian Blue is easily formed in spark-discharge experiments using saline aerosols of ferrous salts [10].…”

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confidence: 96%

Thermal Wet Decomposition of Prussian Blue: Implications for Prebiotic Chemistry

Ruíz-Bermejo

Rogero

Menor‐Salván

et al. 2009

Chemistry & Biodiversity

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The complex salt named Prussian Blue, Fe4[Fe(CN)6]3 x 15 H2O, can release cyanide at pH > 10. From the point of view of the origin of life, this fact is of interest, since the oligomers of HCN, formed in the presence of ammonium or amines, leads to a variety of biomolecules. In this work, for the first time, the thermal wet decomposition of Prussian Blue was studied. To establish the influence of temperature and reaction time on the ability of Prussian Blue to release cyanide and to subsequently generate other compounds, suspensions of Prussian Blue were heated at temperatures from room temperature to 150 degrees at pH 12 in NH3 environment for several days. The NH3 wet decomposition of Prussian Blue generated hematite, alpha-Fe2O3, the soluble complex salt (NH4)4[Fe(CN6)] x 1.5 H2O, and several organic compounds, the nature and yield of which depend on the experimental conditions. Urea, lactic acid, 5,5-dimethylhydantoin, and several amino acids and carboxylic acids were identified by their trimethylsilyl (TMS) derivatives. HCN, cyanogen (C2N2), and formamide (HCONH2) were detected in the gas phase by GC/MS analysis.

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“…As most of the double metal cyanide (DMC) complexes are insoluble in water, it is reasonable to assume that they might have locally settled at the bottom of the sea or at its shores. The presence of transition metal ions in primordial oceans was reported by Kobayashi and Ponnamperuma [8], while the formation of cyanides in several simulated experiments [9,10] showed that cyanide ions might have reacted with the available transition metal ions, thus forming a number of double metal cyanide complexes.…”

Section: Introductionmentioning

confidence: 99%

Adsorption and Oxidation of Aromatic Amines on Metal(II) Hexacyanocobaltate(III) Complexes: Implication for Oligomerization of Exotic Aromatic Compounds

et al. 2017

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Based on the hypothesis on the presence of double metal cyanides in the primordial oceans, a series of nano-sized metal(II) hexacyanocobaltate(III) (MHCCo) with the general formula: M 3 [Co(CN) 6 ] 2 ·xH 2 O (where M = Zn, Fe, Ni and Mn) has been synthesized. Surface interaction of aromatic amines, namely aniline, 4-chloroaniline, 4-methylaniline and 4-methoxyaniline with MHCCo particles has been carried out at the concentration range of 100-400 µM at pH~7.0. The percentage binding of aromatic amines on MHCCo surface was found to be in the range of 84%-44%. The trend in adsorption was in accordance to the relative basicity of the studied amines. At the experimental pH, amines reacted rapidly with the surface of the iron(II) hexacyanocobaltate, producing colored products that were analyzed by Gas Chromatography Mass Spectroscopy (GC-MS). GC-MS analysis of the colored products demonstrated the formation of dimers of the studied aromatic amines. Surface interaction of aromatic amines with MHCCo was studied by Fourier Transform Infrared (FT-IR) spectroscopy and Field Emission Scanning Electron Microscopy (FE-SEM). The change in amine characteristic frequencies, as observed by FT-IR, suggests that interaction took place through the NH 2 group on amines with metal ions of hexacyanocobaltate complexes. FE-SEM studies revealed the adherence of 4-methoxyaniline on zinc hexacyanocobaltate particles surface. We proposed that MHCCo might have been formed under the conditions on primitive Earth and may be regarded as an important candidate for concentrating organic molecules through the adsorption process.

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Was ferrocyanide a prebiotic reagent?

Cited by 71 publications

References 29 publications

Prebiotic chemistry: a new modus operandi

Prebiotic chemistry: a new modus operandi

Thermal Wet Decomposition of Prussian Blue: Implications for Prebiotic Chemistry

Adsorption and Oxidation of Aromatic Amines on Metal(II) Hexacyanocobaltate(III) Complexes: Implication for Oligomerization of Exotic Aromatic Compounds

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