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Prussian Blue as Prebiotic Reagent

Article · December 2009

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Marta Ruiz-Bermejo Cesar Menor Salvan

Centro de Astrobiología University of Alcalá
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Bioastronomy 2007: Molecules, Microbes, and Extraterrestrial Life
ASP Conference Series, Vol. 420, 2009
K. J. Meech, J. V. Keane, M. J. Mumma, J. L. Siefert, and D. J. Werthimer, eds.

Prussian Blue as a Prebiotic Reagent

M. Ruiz-Bermejo, C. Menor-Salván, S. Osuna-Esteban, and

S. Veintemillas-Verdaguer
Centro de Astrobiologı́a [Consejo Superior de Investigaciones
Cientı́ficas-Instituto Nacional de Técnica Aeroespacial (CSIC-INTA)].
Carretera Torrejón-Ajalvir, Km. 4,2. E-28850 Torrejón de Ardoz,
Madrid, Spain.

Abstract. Ferrocyanide has been proposed as a potential prebiotic reagent

and the complex salt Prussian Blue, Fe4 [Fe(CN)6 ]3 , might be an important reser-
voir of HCN, in the early Earth. HCN is considered the main precursor of amino
acids and purine and pyrimidine bases under prebiotic conditions. Recently, we
observed the formation of Prussian Blue in spark discharge experiments using
saline solutions of ferrous chloride, FeCl2 . Using Prussian Blue as starting ma-
terial in ammonium suspensions, we obtained organic compounds containing ni-
trogen. These results seem to indicate that Prussian Blue could have been first,
a sink of HCN, and then in subsequent reactions, triggered by pH fluctuations,
it might have lead to organic life precursors.

1. Introduction

Hydrogen cyanide (HCN) is ubiquitous in the Universe. HCN has been iden-
tified in the gas phase of the interstellar medium as well as in comets, in the
atmosphere of planets and on the surface of moons. HCN is one of the main
products obtained in prebiotic synthesis experiments with spark discharge, UV
irradiation and laser shock on various gas mixtures (Chen and Chen 2005; Sal-
adino et al. 2004). Several experiments suggest that HCN could have served
as a prebiotic precursor of purines, pyrimidines, and amino acids, as well as of
others compounds such as oxalic acid and guanine. Concentrated solutions of
HCN produce, by polymerization, nucleic acid bases and amino acids, whereas
in dilute solutions (< 0.01 M) hydrolysis becomes dominant. At lower concen-
tration in the primitive ocean, hydrolysis of HCN should be predominant to
form ammonia and formic acid. Therefore, if HCN polymerization was actually
important for the production of the first and essential biomolecules, there must
have been routes by which dilute HCN solutions were concentrated. Some iron
derivatives, such as ferrocyanide [Fe(CN) 6 ]−4 and the insoluble complex salt
Prussian Blue, Fe4 [Fe(CN)6 ]3 [ferric hexacyaneferrate (II)], have been proposed
as intermediates to store HCN in the primitive Earth (Arrhenius et al. 1994).
In a recent work, we have demonstrated that Prussian Blue is easily formed
under plausible prebiotic conditions using spark discharges, an CH 4 /N2 /H2 at-
mosphere and saline solutions of ferrous salts (Ruiz-Bermejo et al. 2007). At 4
< pH < 10, Prussian Blue is a stable and insoluble compound but outside that
interval it can undergo solubilization, releasing cyanide. Oxidizing or highly
171
172 Ruiz-Bermejo et al.

reductive mediums as well as ultraviolet light could also lead to unstabilization

of Prussian Blue. Here, we report the first results on the synthesis of organic
compounds from Prussian Blue in ammonium solutions in conditions-like Oró
for the synthesis of adenine (Oró and Kimball 1961).

2. Experimental Process

Suspensions of Fe4 [Fe(CN)6 ]3 in NH4 OH were heated at 70 o C, 100 o C, 130 o C

and 150 o C during 24 h, 48 h and 1 week. All samples were centrifuged after
the time of reaction, and the supernatant separated from the insoluble solid
(mixture of iron hydroxides plus unreacted Prussian Blue). The supernatants
were chromatographied using flash grade silica gel. In all cases, two fractions
were colleted. Both fractions were dried by reduced pressure, yielding a white
solid for the first fraction and a yellow solid for the second one. The white solids
were analyzed for nucleic acid bases and carboxylic acids by GC-MS of their
trimethylsilyl derivatives (Ruiz-Bermejo et al. 2007). For each reaction, the IR
spectra of both solids were recovered in CsI pellet on the reflectance mode of
operation.

3. Results

In all experiments, the IR spectra of the reaction raws are similar and show
strong differences with respect to the Prussian Blue IR spectrum (Figure 1).
The IR spectra of the fraction 1 and fraction 2 present bands at 2044-2032
cm that can be related to -CN groups and R-C=C=NH. The signal at 2119
−1

cm−1 can be assigned to N=C=O or N=C=N or -N≡C groups. The features at

1760-1660 cm−1 may be associated with C=O and C=N bonds, and the bands
at 3128 and 1409 cm−1 with the ammonium cation (NH4 + ).
In addition, the fraction 1 and fraction 2 were analized by ICP-Mass spec-
trometry. The fraction 1 is an organic mixture free on iron but the fraction 2
contains a 31% of iron. Thus, regarding these results with the IR spectra, it
seems that fraction 2 is formed, among others, by iron complexes containing
-CN groups (for example for the soluble salt K 4 [Fe(CN)]6 the band related to
nitrile groups appears at 2042 cm −1 ) and that fraction 1 is an organic complex
solid formed by compounds rich in nitrogen and unsaturations but not nitriles.
Under all conditions assayed, organic compounds containing nitrogen were
detected by GC-MS (Table 1), in good agreement with the spectroscopy data.
The production of urea, dimethylhydantoin, and some carboxylic acid seems to
improve at 100 o C with reaction time between 24 and 48h.
It is interesting to point out the formation of hydantoin derivatives since
these compounds are precursors of α-amino acids and potentially intermediates
in the prebiotic synthesis of peptides (Taillades et al. 1998) and the detection of
sugar related compounds such as glycerol and lactic acid.
 Prussian Blue as a Prebiotic Reagent 173

Figure 1. Figure 1. a) IR spectrum of Prussian Blue. IR spectra of the

reaction heating at 100 C during 168 h. b) Reaction raw. c) Fraction 1. d)
Fraction 2.

4. Conclusions

• Iron could act as a scavenger and concentrator of HCN in the prebiotic

hydrophere.

• The pH-modulated release of cyanide from Prussian Blue in the presence

of ammonia leads to the synthesis of organic compounds rich in nitrogen.

• The formation of Prussian Blue lowers the fixation of HCN like insol-
uble HCN polymers and favour the synthesis of single nitrogen organic
molecules, such as hydantoin.
 174 Ruiz-Bermejo et al.

Table 1. Reaction conditions and organic compounds collected from Prus-

sian Blue.
T (o C) t (h) MSTFA (derivatives)
70 24 Urea, lactic acid
70 48 Urea, lactic acid, glycerol
70 168 Urea, lactic acid
100 24 Urea, lactic acid, glycerol, dimethylhydantoin, malic acid
100 48 Urea, dimethylhydantoin, 2-hydroxy-2-methyl-propionic acid
100 168 Urea, lactic acid, unknown amino acid, glycerol, glycine
130 24 Urea, dimethylhydantoin, 2-aminoisobutyric acid
130 48 Urea
130 168 Urea, lactic acid, glycerol, unknown amino acid
150 24 Urea, glycine
150 48 Urea, glycerol
150 168 Lactic acid, 2-hydroxybutiric acid, glycerol

• Sugar related compounds were obtained under relatively mild conditions

using Prussian blue as precursor.

Acknowledgments. The authors have used the research facilities of Cen-

tro de Astrobiologı́a (CAB) and have been supported by Instituto Nacional
de Técnica Aeroespacial Esteban Terradas (INTA) and the project AYA2006-
15648-C02-02 of the Ministerio of Educación y Ciencia (Spain). We also thank
M.-P. Zorzano for her valuable comments.

References

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