Geochemical Sources and Availability of Amidophosphates on the Early Earth

Article abstract of DOI:10.1002/anie.201903808

Phosphorylation of (pre)biotically relevant molecules in aqueous medium has recently been demonstrated using water-soluble diamidophosphate (DAP). Questions arise relating to the prebiotic availability of DAP and other amidophosphosphorus species on the early earth. Herein, we demonstrate that DAP and other amino-derivatives of phosphates/phosphite are generated when Fe₃P (proxy for mineral schreibersite), condensed phosphates, and reduced oxidation state phosphorus compounds, which could have been available on early earth, are exposed to aqueous ammonia solutions. DAP is shown to remain in aqueous solution under conditions where phosphate is precipitated out by divalent metals. These results show that nitrogenated analogues of phosphate and reduced phosphite species can be produced and remain in solution, overcoming the thermodynamic barrier for phosphorylation in water, increasing the possibility that abiotic phosphorylation reactions occurred in aqueous environments on early earth.

Full text of DOI:10.1002/anie.201903808

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Accepted Article
Title: Geochemical Sources and Availability of Amidophosphates on
the Early Earth
Authors: Clémentine Gibard, Eddy I Jiménez, Terence Kee,
Ramanarayanan Krishnamurthy, and Matthew Pasek
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201903808
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10.1002/anie.201903808
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Geochemical Sources and Availability of Amidophosphates on
the Early Earth
Clémentine Gibard[a], Ian B. Gorrell[b], Eddy I. Jiménez[a], Terence P. Kee*[b], Matthew A. Pasek*[c],
Ramanarayanan Krishnamurthy*[a]
O
Abstract: Phosphorylation of (pre)biotically relevant molecules in
aqueous medium leading to sugar-phosphates, (oligo)nucleotides,
(oligo)peptides and lipids/vesicles has recently been demonstrated
by the use of water-soluble diamidophosphate (DAP). Naturally,
questions arise relating to the prebiotic plausibility and availability of
DAP and other amidophosphosphorus species on the early earth.
Herein, we demonstrate that DAP and other amino-derivatives of
phosphates/phosphite are generated when Fe3P (surrogate of
mineral schreibersite), condensed phosphates and reduced
oxidation state phosphorus compounds that could be available on
early earth are exposed to aqueous ammonia solutions. Additionally,
DAP is shown to remain in aqueous solution under conditions where
phosphate is precipitated out by divalent metals. These results show,
for the first time, that nitrogenated analogs of phosphate and
reduced phosphite species can be produced (alongside the usual
oxygenated versions) and remain in solution, which increase the
potential for abiotic phosphorylation reactions by overcoming the
thermodynamic barrier in water.
O
P
O–
P
O
P
–O
O
P
–O
O
P
–O
P
O
P
H2N
–O
2
NH2
NH4OH
ref [3]
NH4OH
–O
O
O–
H2N
O
O
O
O
O
O–
+
O
O
P
–O
P
–O
1
–O
O–
O
cyclo-trimetaphosphate
pyrophosphate
OH
OH
O
O
OH
OH
1 or 2
+ pyranose form
ref [4]
O
O
HO
OH
OH
P
–O
O
HO
O
A, U, G, C
O
U (A, G, C)
2
oligonucleotides
ref [5]
HO
OH
O
O
P
–O
O
R
R
2
2–
H2N
HO
CO2H
+
oligopeptides
vesicles
OPO3
H2N
ref [5]
O
O
O
2
OH
HO
O
O
O
7
O
7
ref [5]
OH
P
O–
Prebiotic phosphorylation in the context of origin of life studies,
by phosphates in aqueous medium, is challenging.[1] It was
recently shown that, instead, by the use of nitrogenous-versions
of phosphates (PN, amidophosphates, which could be
generated from condensed phosphates, Scheme 1, top), the
thermodynamic barrier of phosphorylation in water could be
overcome.[2] For example, sugars could be phosphorylated
efficiently in water by the use of amidotriphosphate[3] 1 and
diamidophosphate (DAP, 2, Scheme 1).[4] Furthermore, DAP
was shown to phosphorylate, in aqueous medium, a suite of
(pre)biotically relevant building blocks (nucleosides, amino acids,
fatty acids and glycerol) leading to the respective oligomeric or
supramolecular self-assembled products (Scheme 1).[5]
Combining this prebiotic phosphorylation proclivity of
amidophosphates with the significance of nitrogenous-
phosphate intermediates in biochemical phosphorylation
pathways, it was argued that amidophosphates (along with
phosphates) should be considered as plausible prebiotic
reactants – raising the question of what would be the prebiotic
sources of amidophosphates.[2] In this context, we show here
Scheme 1. The phosphorylation capabilities of amidophosphates 1 and 2
under aqueous or moist-paste conditions.
that P-containing Fe3P (analog of mineral schreibersite[6] that is
present in meteorites), condensed phosphates (P4O10)[7] and
phosphite[1] 5 that could be present on early earth, react with
aqueous ammonia to yield various nitrogenous derivatives of
phosphates
and
phosphites,
such
as
DAP,
monoamidophosphate (MAP, 3) and amidophosphite, 4 a new
species that has been previously hypothesized[2].
Inspired by the observations that schreibersite was corroded
in the presence of water to produce phosphates[6], we
hypothesized that if aqueous NH4OH was used it may lead to
amidophosphates (Scheme 2). Two experiments (one under air
and the other under argon) were setup wherein Fe3P (which is
an acceptable surrogate to meteoritic schreibersite)[6b] was
treated with 25% aq. NH4OH and monitored by 31P-NMR. Within
a few days, signals around 3.8, 6.2 and 8.8 ppm were observed
in the inert atmosphere reaction apart from the formation of
phosphite 5 at 3.7 ppm (Supplementary, Fig. S3). Spiking the
sample with MAP suggested the peak at 8.8 ppm could be MAP,
3 (Fig. S4). After 12 days, a new peak at 14 ppm was observed,
which corresponded to DAP, 2 – as also suggested by spiking
with DAP (Fig. S5). Repeating the experiment and taking
overnight 31P-NMR scans we observed (Fig. 1a) not only DAP
and MAP, but also a new species, monoamidophosphite 4, the
nitrogenous analog of phosphite. We also observed phosphate 6
and phosphite 5 as corroborated by the H-coupled 31P-NMR.
Very weak 31P-NMR signals were observed for the reaction
under air (possibly due to O2 quenching radical reactions
occurring within or near the mineral[6]); therefore, all our further
experiments were performed under inert atmosphere (Figs. S3
and S6).
[a]
Dr. Clémentine Gibard, Dr. Eddy I. Jiménez,
Prof. Dr. Ramanarayanan Krishnamurthy* Department of Chemistry,
The Scripps Research Institute,
10550 North Torrey Pines Road, La Jolla, CA 92037, USA
E-mail: rkrishna@scripps.edu
[b]
[c]
Dr. Ian B. Gorrell, Prof. Dr. Terence Kee*
School of Chemistry, University of Leeds
Woodhouse lane, Leeds LS2 9JT
E-mail: T.P.Kee@leeds.ac.uk
Prof. Dr. Matthew Pasek*
School of Geosciences, University of South Florida
Tampa, Florida 33620, USA
E-mail: mpasek@usf.edu
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201903808
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within the same time frame by 31P-NMR. At pH 12 we observed
only the oxygenated species as previously reported.[6g] This
suggests that there could be a critical concentration of ammonia
(at least 3% as suggested by this study), or a critical pH needed
for amidophosphates to be generated by the type of chemistries
demonstrated above. This may limit the geographical areas
where such chemistries may occur, an aspect that needs further
investigation. In this context, where schreibersite itself has been
shown to phosphorylate nucleosides, it is of importance to note
that phosphorylation was observed above the equilibrium
concentration only when some nitrogen source was added.[6h] In
fact, the best yield was reported in the presence of NH4OH
suggesting that P-N species may be the species responsible for
phosphorylation. Therefore, it may not be surprising if P-N
species are also involved in many of the previously reported
prebiotic phosphorylation methods that use some form of
nitrogen sources with activation.[2]
O
P
–O
O
P
–O
3
MAP
O
P
–O
O
P
–O
O
P
–O
+
aq. NH3
+
+
+
+
–O
–O
O–
O–
Fe3P
H2N
H2N
H2N
H
NH2
H
2
DAP
5
4
6
aq. NH3
aq. NH3
P4O10
+
+
+
+
3
3
N.D.
2
6
+
+
N.D.
N.D.
+ condensed
phosphates
O
P
–O
N.D.
N.D.
6
+
–O
H
hν (254 nm)
5
Scheme 2. Reactions for producing amidophosphates under various
conditions. Reaction with aqueous ammonia at room temperature (top) with
Fe3P, (middle) with P4O10 and (bottom) with phosphorus acid 5 with irradiation.
N.D. = Not detected.
To prove that indeed the amidated species 2, 3 and 4 are
being formed we repeated the above experiment using 15N-
labeled 25% aq. NH4OH. If the nitrogen is attached to the
phosphate, then further 15N-31P splitting should be observed.
Indeed, as expected (Fig. 1b, c), the signal assigned to DAP 2
was a triplet (J = 16.1 Hz), while the MAP 3 was a doublet (J =
10.2 Hz) and the monoamidophosphite 4 signal was a doublet of
doublets (JH = 576, JN = 6.9 Hz). When the concentration was
lowered to 12.5, 6.3 and 3.2% aq. NH4OH the amidophosphate
species were still observed (Figs. S7-S8) We did not check
lower concentrations due to NMR time constraints. The total
incorporation of nitrogen in the PN species (2+3+4) calculated
from 31P-NMR, under the lower NH3 concentrations, was about 9
through 4% (Table S1), nearly matching the percentage of
ammoniacal nitrogen available in solution – suggesting efficient
reaction of NH3 with Fe3P. The similarity of the NMR at day 6
versus day 20 suggests that the PN species are stable under
these conditions, consistent with known rates of hydrolysis.[8]
We further explored two additional routes for the formation of
amidophosphates via reactions in solution: amidation of high
energy condensed phosphates, and radical recombinations
leading to N-P bonds. In the first approach, P4O10 was slowly
added to a solution of 25% aq. NH4OH. The compound P4O10
has been hypothesized to be formed in dry volcanic vent
environments[7], based on the presence of di- and tri-phosphate
in vent fluids. Were this compound formed through volcanic
action, then its interaction with ammonium-bearing fluids on the
early earth could yield amidophosphates, akin to the reaction of
ammonia with trimetaphosphate.[3]
Amidophosphates were
formed by amidation of P4O10, forming PN bonds at the
monomer level at about 14% of the total newly formed N-P and
O-P bonds (Fig. S13). As in the case for the reaction with Fe3P,
the amount of PN bond formation corresponded closely to the
amount of N in solution. In the absence of ammonium, only
phosphate and polyphosphates (pyro-, tri-, trimeta- and others)
are formed.
Considering the constraints imposed by the plausible
sources and availability of ammonia on early earth[9], we briefly
explored aqueous NH4Cl (25% by weight) as a source at various
pHs (4, 8.5, 10 and 12) but did not observe any PN species
A
follow-up reaction investigated the formation of
amidophosphate by UV-light (254 nm) irradiation
of a solution of phosphorus acid (1 M) in 25% aq.
NH4OH in H2O (Scheme 2). After about 2 weeks
of irradiation about 1% of the phosphorus acid
oxidized to produce primarily phosphoric acid, but
also MAP 3 (~3% of the oxidized product, Fig.
4
5
3
6
2
a) 14N-, 1H-decoupled
O
P
S14).
These results confirm the stability of
O
P
–O
H2N
H
phosphite towards oxidation, as suggested
previously.[10] Parallel radiative processes were
O
P
–O
O–
H2N
H2N
NH2
–O
explored
using
NH3
and
H2O-generated
b) 15N-, 1H-decoupled
microwave plasma experiments, similar to those
used previously.[6b] With Na2HPO3, Na2HPO2 and
Fe3P as substrates and H2O-NH3-Ar plasma’s (55
W, ca 5% v/v NH3, 90 mins) we were unable to
confirm the presence of PN compounds, although
control reactions demonstrated that the expected
PO compounds were present when just a H2O-Ar
plasma was used (see SI, Figs. S1-S2, Table S3).
c) 15N-, 1H-coupled
ppm
Figure 1. 31P NMR spectra of reaction mxiture of Fe3P in 25% aqueous ammonia at room temperature for 12 days. Top spectrum shows the H-decoupled NMR
with unlabeled aq.14NH3. Middle spectrum shows H-decoupled NMR with labeled aq.15NH3. The bottom spectrum show the H-coupled NMR with labeled aq.15NH3.
The coupled signals (doublets and triplet) are the result of the 15N-31P coupling signifying the formation of amido-phosphate and phosphite species.
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phosphono acetic acid
(internal standard)
2- 6
PO4
DAP
2
Figure 2. Effects of divalent metals on the availability of
DAP versus orthophosphate in solution as monitored by
31P NMR spectra after 15 min. Phosphonoacetic acid (18.4
2-
a)
DAP + PO4
1.0
1.0
1.0
1.0
1.0
0.8
1.3
ppm) was used as internal standard placed within
a
capillary. a) spectrum of 0.5 M DAP/Na2HPO4 (1:1); b) with
1.0 M, 2 equiv. MgCl2; c) with 1.0 M 2 equiv. CaCl2; d) with
1.0 M 2 equiv. ZnCl2; and e) with synthetic sea water with
0.8 M Mg+2 and 0.15M Ca+2 (see table S4). The values
under the NMR peak refer to the integration values.
b) + 2 eq. Zn+2
0.3
0.0
+ 2 eq. Ca+2
c)
0.7
0.0
ammonia-bearing solutions. For instance, as
stated earlier, the hydrolysis of P4O10 releases
about 105 kJ/mol of P hydrolysed (a majority
released within the first three hydrolytic steps),
enough to also allow for amidation. In addition,
the oxidation of schreibersite by water to
phosphate, FeO and H2 gas releases about 100
kJ/mol of P, more than enough to overcome any
amidation energy barrier. The oxidation of
+ 2 eq. Mg+2
d)
e)
0.6
0.1
+ synthetic
seawater
0.4
0.0
ppm
phosphite to phosphate via water (H2 as a product) also
produces about 55 kJ/mol of P, in addition to the UV energy
added.
A contrasting property of amidophosphate (such as DAP 2),
when compared to its oxygenated orthophosphate counterpart
(6), is the lower number of negative charges, suggesting that it
may be less prone to precipitation by divalent metals. To test
this possibility, we monitored solutions of DAP
2
and
orthophosphate 6 in the presence of CaCl2, MgCl2, ZnCl2 and
seawater by 31P-NMR. In each case, DAP was still present in
solution while the intensity of 6 had greatly diminished or
completely vanished due to precipitation (Fig 2 and Figs. S9-
S12). In the case of seawater experiment, we titrated an
increasing amount of seawater salt and found that at
concentrations where the phosphate was completely
precipitated out, DAP still remained in solution (Table S4 and Fig.
S15). Taken together, these results imply that amidophosphate
species could be available in solution for phosphorylation
reaction, more than orthophosphates, and provide a way out of
the “phosphate problem”.[11]
Figure 3. Stability diagram for P-O and P-N species with varying water and
ammonia activities (note logarithmic scale). Activities of each compound were
assumed to be 1, with the temperature set at 298 K and 1 atm. of pressure.
With the results of these experiments in mind, we
investigated the thermodynamics of amidophosphate formation.
Data was supplemented from the HSC program,[12] though for
monoamidophosphate and diamidophosphate data are
limited. However, the formation of DAP and MAP from the
amidation of P4O10 and trimetaphosphate,[13] and the lack of
formation of DAP and MAP from amidation of triphosphate and
pyrophosphate, provides reasonable constraints on the
formation of P-N bonds. The hydrolysis of P4O10 to H3PO4
releases about 420 kJ/mol, or about 70 kJ/mol for each bond
hydrolyzed, and the hydrolytic opening of the trimetaphosphate
ring is about 40 kJ/mol.[14] The hydrolysis of triphosphate and
pyrophosphate release about 20 kJ/mol,[1] suggesting the
hydrolysis of amidophosphates is about 30 kJ/mol. Using this
assumption, we calculate the range of stability of various N-P-O-
These results suggest that high energy P sources produce
amidophosphates. Furthermore, given that the energy provided
per
P liberated greatly exceeds the energy barrier for
amidophosphate formation for schreibersite oxidation and P4O10
hydrolysis, it comes as no great surprise that the formation of
amidophosphates relative to phosphates in these two cases is
close to the proportion of N/O in the reactive solutions. In other
words, the formation of amidophosphates is due to a kinetic
process principally involving whatever nucleophile happens to
be nearby, as opposed to a thermodynamics-driven process. In
the case of UV photolysis, the lower free energy available
means that thermodynamics play a more important role, and
hence less amidophosphates (relative to phosphates) are
formed. Based on these considerations, coupled with previously
proposed pathways for the aqueous corrosion of schreibersite[6]
H
compounds
(Fig.
3). Notably,
the
presence
of
amidophosphates should be limited primarily to low water-
activity and high ammonia-activity conditions, as might be
expected. The formation of amidophosphates hence requires
the addition of energy in aqueous solution. This energy addition
is accomplished by changes to P speciation upon reaction with
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a)
Acknowledgements
2 x
4–
O3PPO3
H2O
2–
Fe3P
PO3
O
P
–O
This work was supported by the Simons Collaboration on the
Origins of Life (327124 to RK) and by NASA Exobiology
(80NSSCC18K1288 to MAP).
2 x
NH3
3–
–
PO3
O–
PO
H2N
+
3
H2
OH–
H+
3
2–
2–
HPO3
HPO4
Keywords: Prebiotic Chemistry • Phosphorylation •
Diamidophosphate • Early Earth • Amidophosphate
b)
O
P
–O
O
P
O–
O
P
O–
O
P
O–
NH3 / H2O
H2
2 x
NH3
H2N
NH2
NH2
Fe3P
+
NH2
NH2
[1]
M. A. Pasek, T. P. Kee, in Origins of Life: The Primal Self-Organization
(Eds.: R. Egel, D.-H. Lankenau, Y. A. Mulkidjanian), Springer Berlin
Heidelberg, Berlin, Heidelberg, 2011, pp. 57-84.
2
DAP
H+
OH–
[2]
[3]
M. Karki, C. Gibard, S. Bhowmik, R. Krishnamurthy, Life 2017, 7, 32.
O. T. Quimby, T. J. Flautt, Zeit. Anorgan. allgemeine Chemie 1958, 296,
220-228.
O
P
–O
O
P
–O
O–
H2N
H2N
H
[4]
[5]
[6]
R. Krishnamurthy, S. Guntha, A. Eschenmoser, Angew. Chem. Int. Ed.
2000, 39, 2281-2285.
3
4
C. Gibard, S. Bhowmik, M. Karki, E.-K. Kim, R. Krishnamurthy, Nat.
Chem. 2018, 10, 212-217.
Scheme 3. The proposed mechanistic pathways for the production of
amidophosphorus species 2, 3 and 4 by corrosion of schreibersite by aqueous
ammonia This is based on previous studies[6] and thermodynamic
considerations discussed below (see also Fig. S16). Additionally, the failure of
the reaction under air may indicate interference in the radical chemistry by O2.
a) M. A. Pasek, Geosci. Front. 2017, 8, 329-335; b) N. L. La Cruz, D.
Qasim, H. Abbott-Lyon, C. Pirim, A. D. McKee, T. Orlando, M. Gull, D.
Lindsay, M. A. Pasek, Phys.Chem. Chemi. Phys. 2016, 18, 20160-
20167; c) D. E. Bryant, D. Greenfield, R. D. Walshaw, B. R. G.
Johnson, B. Herschy, C. Smith, M. A. Pasek, R. Telford, I. Scowen, T.
Munshi, H. G. M. Edwards, C. R. Cousins, I. A. Crawford, T. P Kee,
Geochem. Cosmochem. Acta 2013, 109, 90-112. d) D. E. Bryant, T. P.
Kee, Chem. Commun. 2006, 2344-2346; f) N. G. Holm, A. Neubeck,
Geochem. Trans. 2009, 10, 9-9; g) M. A. Pasek, D. S. Lauretta,
Astrobiology, 2005, 5, 515-535; h) M. Gull, M. A. Mojica, F. M.
Fernández, D. A. Gaul, T. M. Orlando, C. L. Liotta, M. A. Pasek, Sci.
Rep. 5, 17198, 2015.
we outline
a plausible mechanism for the formation of
amidophosphates (Scheme 3). Some of the predictions of what
species will be formed from this mechanism matches well with
the observations (Fig. S16). Using the data above, we evaluated
the three potential sources of amidophosphates for geochemical
relevance (see SI, page S18 for detailed assumptions and
calculations and Table S5): schreibersite, volcanic P4O10, and
[7]
a) Y. Yamagata, H. Watanabe, M. Saitoh, T. Namba, Nature 1991, 352,
516-519; b) M. A. Pasek, T. P. Kee, D. E. Bryant, A. A. Pavlov, J. I.
Lunine, Angew. Chem. Int. Ed. 2008, 47, 7918-7920; C) S. Johansson,
C. Kuhlmann, J. Weber, T. Paululat, C. Engelhard, J.S. auf der Günne,
Chem. Comm. 2018, 54, 7605-7608.
reduced oxidation state
P
compounds. It is especially
noteworthy that the P4O10 system affords both PN and PO
phosphorylating molecules, both classes being capable of
phosphorylating organics under different physicochemical
conditions; a scenario that contemporary cellular biology also
adopts. Of these, we find that all three could have been relevant
to early earth conditions, each generating 1015-1019 moles of
amidophosphates over the first billion years of earth’s history.
These data are the first for a planetary environment and
complement the observations of PN species in interstellar
medium (ISM) diffuse clouds and star-forming regions.[15]
[8]
[9]
Von S. Richter, W. Tøopelman, H.-A. Lehman, Z. Anorg. Allg. Chem.
1976, 424, 133-143.
a) J. P. Ferris, D. E. Nicodem, Origin Life Evol. Biochem. 1974, 107-
117; b) D. P. Summers, Orig. Life Evol. Biosph. 1999, 29, 33-46; c) D.
P. Summers, S. Chang, Nature 1993, 365, 630-633; d) J. A. Brandes, N.
Z. Boctor, G. D. Cody, B. A. Cooper, R. M. Hazen, H. S. Yoder, Nature
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Holland, J. L. Yarger, Proc. Nat. Acad. Sci. U.S.A 2011, 108, 4303-
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Schlesinger, S. L. Miller, J. Mol. Evol. 1983, 19, 383-390. h) S. M. Som,
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K. J. Zahnle, J. Geophys. Res. Atm. 1986 91, 2819-2834.
In summary we have shown that there could be reasonable
pathways to various nitrogenated phosphorus (PN) compounds
(amidophosphates) that could have been generated and
coexisted with the oxygenated counterparts (phosphates) –
provided ammonia could have been available at critical
concentrations[9] – in an early earth scenario. This suggests that
amidophosphates may have been present in some abundance
as a prebiotic reagent on the early earth and could alleviate the
problems associated with phosphorylation in aqueous medium.
[10] B. Herschy, S. J. Chang, R. Blake, A. Lepland, H. Abbott-Lyon, J.
Sampson, Z. Atlas, T. P. Kee, M. A. Pasek, Nat. Commun. 2018, 9,
1346.
[11] A. W. Schwartz, Philos. Trans. R. Soc., B 2006, 361, 1743-1749.
[12] M. Pasek, Current Opinion in Chem. Biol. 2019, 49, 53-58.
[13] R. Krishnamurthy, G. Arrhenius, A. Eschenmoser, Orig. Life Evol.
Biosph. 1999, 29, 333-354.
Experimental Section
[14] O. Meyerhof, R. Shatas, A. Kaplan, Biochim. Biophys. Acta 1953, 12,
121-127.
See supporting information for description of experimental methods,
NMR data, calculations for thermodynamics of amidophosphate
formation and geochemical availability of sources for amidophosphates.
[15] a) E. Macia, Chem.Soc. Rev. 2005, 34, 691-701; b) B. Fegley, J. S.
Lewis, Icarus 1980, 41, 439-455; c) E. C. Sutton, G. Blake, C. R.
Masson, T. Phillips, The Astrophys. J. Supplement Series 1985, 58,
341-378; d) L. M Ziurys, Astrophys. J. 1987, 321, L81-85.
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Entry for the Table of Contents
COMMUNICATION
Clémentine Gibard, Ian B. Gorrell, Eddy
I. Jiménez, Terence P. Kee*, Matthew A.
Pasek*, Ramanarayanan
Fe3P
O
P
–O
O
P
–O
O
O
P
–O
O
P
–O
aq. NH3
P
–O
P4O10
–O
O–
H2N
H2N
O–
H
NH2
H2N
–O
H
H2O
Krishnamurthy*
H3PO3
(hν)
Page No. – Page No.
Geochemical Sources and Availability
of Amidophosphates on the Early
Earth
Amidophosphates are produced by the same pathways that give rise to phosphates
from various phosphorus sources when reacted with aqueous ammonia.
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