ASTROBIOLOGY
Volume 9, Number 2, 2009
© Mary Ann Liebert, Inc.
DOI: 10.1089/ast.2007.0143
Research Article
Role of Metal Oxides in Chemical Evolution:
Interaction of Ribose Nucleotides with Alumina
Avnish Kumar Arora and Kamaluddin
Abstract
Abstract
Interaction of ribonucleotides—namely, 5-AMP, 5-GMP, 5-CMP, and 5-UMP—with acidic, neutral, and ba-
sic alumina has been studied. Purine nucleotides showed higher adsorption on alumina in comparison with
pyrimidine nucleotides under acidic conditions. Adsorption data obtained followed Langmuir adsorption
isotherm, and Xm and KL values were calculated. On the basis of infrared spectral studies of ribonucleotides,
alumina, and ribonucleotide-alumina adducts, we propose that the nitrogen base and phosphate moiety of the
ribonucleotides interact with the positive charge surface of alumina. Results of the present study may indicate
the importance of alumina in concentrating organic molecules from dilute aqueous solutions in primeval seas
in the course of chemical evolution on Earth. Key Words: Chemical evolution—Origin of life—Metal oxides—
Alumina—Ribonucleotides. Astrobiology 9, 165–171.
1. Introduction has a rhombohedral structure similar to Cr2O3, -Fe2O3, and
Ti2O3. It is likely that alumina was present on primitive Earth
I T HAS BEEN PROPOSED that a catalyst played a central role in
the formation of biopolymers during the course of chem-
ical evolution and origin of life. Catalysts tend to direct the
and catalyzed various reactions. Prebiotic synthesis of
purine, adenine, cytosine, and 4(3H)-pyrimidinone from
formamide has been found to be catalyzed by alumina, as
reaction along a few reaction pathways, so that only a lim- well as other oxides and minerals, and its application in the
ited array of products is obtained. Catalysts bind specific origin of life has been discussed (Saladino et al., 2001). Un-
types of compounds to their surfaces and then convert them der mild conditions, alumina is found to catalyze peptide
to a limited number of products. The involvement of clays formation (Basiuk and Sainz-Rojas, 2001). Meng et al. (2004)
and other inorganic minerals in adsorption and catalytic re- examined adsorption and thermal condensation of glycine
actions of biomolecules in molecular evolution was first pro- on silica, and Tzvetkov et al. (2004) studied the interaction
posed by Bernal (Bernal, 1951). Ferris studied the role of clays between glycine and alumina.
in catalyzing reactions of nucleotides (Ferris and Hagan, We propose that alumina and other metal oxides on prim-
1986; Ferris et al., 1989, 1990; Ferris and Ertem, 1992; Ertem itive Earth may have provided surfaces onto which bio-
and Ferris, 1997). The availability and relevance of soluble monomers could have concentrated through selective ad-
mineral salts in a primordial environment was proposed by sorption. In this work, we have studied the interaction of the
Lahav and Chang (Lahav and Chang, 1976, 1982) and Lahav ribonucleotides 5-AMP, 5-GMP, 5-CMP and 5-UMP with
and White (Lahav and White, 1980). aluminum oxide, which is an important subject in view of
Aluminum is an important component of clay on Earth, the expected low concentrations of these compounds in
where it is coordinated with oxygen and exists in octahedral aqueous solutions and the associated problem of their poly-
form. The existence of alumina on Mars has also been re- merization during the course of chemical evolution. Ribose
ported (Keener, 1997). Alumina is found as a mineral and nucleotides have negatively charged phosphate groups, lone
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, India.
165
166 ARORA AND KAMALUDDIN
pair that contain nitrogen atoms, and aromatic rings with on acidic, neutral, and basic alumina. All three forms of alu-
electron clouds. So interaction might have taken place with mina are equivalent with respect to nucleotide adsorption
the negatively charged moieties of nucleotide and the posi- and were verified by putting any one of them in the condi-
tively charged surface of alumina. The present work shows tions of desired pH. Adsorption isotherms were obtained by
aluminum oxide to be a good adsorbent for ribonucleotides plotting the amount of nucleotides adsorbed, Xe (mg/g), ver-
and, therefore, supports the possible role of metal oxides in sus their equilibrium concentration, Ce (mol L1). Plots were
chemical evolution. made with Origin 6.0 software and were extrapolated toward
the origin of the graph with zero absorbance against zero
2. Experimental concentration of the nucleotides. At extremely low concen-
trations of the nucleotide, estimation of absorbance was very
Materials
difficult. From the adsorption isotherm, percent adsorption
Aluminum oxide acidic [70–290 mesh size, pH of aqueous of nucleotides on the metal oxides was determined, which
suspension 4.5, Sisco Research Laboratories (SRL), Mumbai, is reported in Table 1. Percent binding was calculated from
India], neutral (70–290 mesh size, pH of aqueous suspension absorbance values of nucleotides before and after adsorption
6.40, SRL), basic (70–290 mesh size, pH of aqueous suspen- at the point of the curve where saturation starts. The initial
sion 8.20, SRL), 5-AMP (SRL), 5-CMP (SRL), 5-GMP (SRL), portions of the isotherms show a linear relationship between
and 5-UMP (SRL) were used as received. All other chemi- the amount adsorbed in mg/g and the equilibrium concen-
cals were of analytical reagent grade. tration. At a higher concentration range, saturation phe-
nomenon was observed (Figs. 1–4). The adsorption data were
2.1. Spectral studies fitted in Langmuir adsorption isotherm (Atkins and de
Paula, 2002) as given below.
The electronic spectra of 5-AMP, 5-GMP, 5-CMP, and
5-UMP were recorded with a Shimadzu UV-1601 spec- Ce Ce 1
kL
trophotometer, and their characteristic max values were 259, Xe Xm Xm
254, 278, 262 nm, respectively. The infrared spectra of ad-
where Ce is equilibrium concentration of nucleotide
sorbents, adsorbates, and adsorption adducts were recorded
(mole/liter), Xe is amount of nucleotide adsorbed per gram
in KBr discs on a Perkin Elmer Fourier transform infrared
weight of adsorbent (mg), Xm is amount of nucleotide ad-
spectrophotometer (Model Perkin Elmer-1600 Series).
sorbed at saturation (mg/g), and kL is the Langmuir ad-
sorption constant (L/mg).
2.2. CHN analysis
A typical graph of Ce/Xe vs. Ce was a straight line [Figs.
Carbon, hydrogen, nitrogen analysis of the adduct was 5–8]. From the curve Xm and kL, values were calculated and
carried out on an Elementar Vario ELHI CHNS analyzer. are presented in Table 1. Higher Xm values indicate more
This showed presence of C, H, and N on the surface of alu- amount of nucleotide adsorbed, while KL value is related to
minum oxide. the enthalpy of adsorption.
Adsorption of nucleotides on all three forms of alumina
2.3. BET surface area was found to be maximum in acidic pH (4.0) as compared
to the neutral and basic forms. All three forms of alumina
The BET surface area of the samples was measured by ni-
are equivalent and could be obtained by putting any one of
trogen adsorption isotherms on micromeritics ASAP 2010
them in the conditions of desired pH. Adsorption of all four
(UK). Samples were activated at 473 K for 4 h prior to the
nucleotides in acidic (pH 6.0), neutral (pH 7.0), and ba-
measurement.
sic (pH 8.0) alumina was studied, and the results are shown
in Table 2. Higher adsorption of the nucleotide is in accor-
2.4. Adsorption studies
dance with the surface area of alumina in their three forms.
Adsorption of nucleotides on aluminum oxide was studied
with use of varying concentrations of nucleotides (400–640
M). Twenty-five milligrams of oxide were added to 5 ml of
different concentrations of aqueous solution of nucleotide. TABLE 1. LANGMUIR CONSTANTS FOR ADSORPTION OF
Mixtures were shaken for about 2 minutes. The mixture after NUCLEOTIDES ON ALUMINUM OXIDES
24 h was centrifuged on a REMI R4C centrifuge for 30 min-
Alumina Nucleotide kL (L mg1) Xm (mg/g)
utes at 4500 rpm. Absorbance of the supernatant was noted at
characteristic max of the nucleotide. The concentration of nu- Acidic 5-AMP 9.86 60.60
cleotides after adsorption for 24 h was determined with the 5-GMP 9.53 62.89
help of a calibration curve made by plotting concentration vs. 5-CMP 6.61 38.31
optical density (O.D.) of nucleotides. The amount of nucleo- 5-UMP 7.11 32.26
tide adsorbed was calculated with the absorbance of nucleo- Neutral 5-AMP 9.87 35.33
tide before and after adsorption. Nucleotide-alumina adduct 5-GMP 9.31 41.84
was washed with water, dried, and subjected to IR studies. 5-CMP 5.63 34.48
5-UMP 6.76 29.23
Basic 5-AMP 8.21 28.57
3. Results 5-GMP 9.24 30.76
5-CMP 6.74 28.08
Adsorption of nucleotides on aluminum oxide was stud- 5-UMP 7.10 25.83
ied over a range of concentrations of adsorbate (400–640 M)
RIBONUCLEOTIDE-ALUMINA INTERACTION 167
FIG. 1. Adsorption isotherms for 5-AMP on alumina.
FIG. 2. Adsorption isotherms for 5-GMP on alumina.
FIG. 3. Adsorption isotherms for 5-CMP on alumina. FIG. 4. Adsorption isotherms for 5-UMP on alumina.
FIG. 5. Langmuir isotherm plots for 5-AMP on alumina. FIG. 6. Langmuir isotherm plots for 5-GMP on alumina.
168 ARORA AND KAMALUDDIN
FIG. 7. Langmuir isotherm plots for 5-CMP on alumina. FIG. 8. Langmuir isotherm plots for 5-UMP on alumina.
TABLE 2. PERCENT BINDING OF NUCLEOTIDES ON ALUMINUM OXIDE
Alumina Nucleotide Percent binding
Acidic 5-AMP 71
5-GMP 72
5-CMP 68
5-UMP 59
Neutral 5-AMP 60
5-GMP 60
5-CMP 54
5-UMP 55
Basic 5-AMP 47
5-GMP 47
5-CMP 41
5-UMP 37
O.D. of ribonucleotide before adsorption O.D. of ribonucleotide after adsorption
% Binding 100
O.D. of ribonucleotide before adsorption
Surface area of acidic, neutral, and basic alumina was found teractions. These groups can act as acid or base, depending
to be 146, 127, and 119 m2/g. on the pH of the solution. Zero point charge (ZPC) for alu-
To show that the behavior of the three forms of alumina mina is 8.9 (Huang et al., 1996). In acidic conditions, positive
is the same and pH of the suspension is responsible for the surface charge on alumina is mainly due to the protonated
differing behavior of acidic, neutral, and basic forms, a typ- aluminol group (AlOH2), whereas in alkaline medium be-
ical experiment was carried out where adsorption of 5-AMP yond pH 8.9, the surface of alumina becomes negatively
on all three alumina under acidic, neutral, and basic condi- charged due to the formation of AlO (Forland et al., 1996).
tions was studied. It was found that adsorption of 5-AMP Below ZPC (8.9), interaction with nucleotides may take place
was maximum in acidic, less in neutral, and the least in ba- through negatively charged oxygen atoms in the phosphate
sic medium (Table 3). Percent adsorption values of 5-AMP group, electrons of the aromatic ring, and lone pair of elec-
on the three alumina under acidic, neutral, and basic condi-
tions were nearly equal. In general, alumina was found to
have an extremely high affinity toward ribonucleotides as TABLE 3. PERCENT ADSORPTION OF 5-AMP ON ALUMINA
the extent of surface covered ( kLCe/1 kLCe) was de-
Percent adsorption
termined to be about 100% irrespective of the pH of the
medium. Alumina pH 4.0 pH 7 pH 8.0 pH 11.0
4. Discussion Acidic 72.0 63.0 47.0 4.0
Neutral 71.0 62.0 47.0 3.0
In an aluminum oxide/water system, the OH groups on
Basic 71.0 62.0 47.0 3.0
the solid surface are the most important sites for surface in-
RIBONUCLEOTIDE-ALUMINA INTERACTION 169
FIG. 9. IR spectra of 5-AMP (a), Alumina (b), and 5-AMP-alumina adduct (c). Adsorption performed at pH 4.0.
170 ARORA AND KAMALUDDIN
TABLE 4. TYPICAL INFRARED SPECTRAL FREQUENCIES (CM1) OF RIBONUCLEOTIDES
BEFORE AND AFTER ABSORPTION ON ALUMINUM OXIDE
Ribonucleotides vNH2 vNH vC-O-P
5-AMP 3221* 3343 1647 1084
(3414)* (3482) (1617) (1108)
5-GMP 3143* 3433 1605 1083
(3390)* (3478) (1584) (1099)
5-CMP 3122* 3334 1539 1091
(3275)* (3462) (1530) (1102)
5-UMP 1473 1082
(1468) (1085)
*Values in parentheses indicate typical infrared spectral frequencies after adsorption.
trons on N and O atoms with the positively charged surface Carbon, hydrogen, nitrogen analysis of the AMP-alumina
of alumina. Purines (5-AMP, 5-GMP), which have one more adduct shows 0.604% N, 0.153% H, and 1.045% C on the sur-
ring and lone pair of electrons (N-7), could adsorb more face of acidic alumina. This confirms the presence of AMP
strongly on alumina compared to pyrimidines (5-CMP and on alumina because C:N molar ratio corresponds to that ex-
5-UMP). pected for 5-AMP.
Under different experimental conditions of pH, adsorp-
tion of nucleotides on the alumina surface may occur 5. Conclusion
through different types of interactions. Negatively charged Alumina may have played a role in selectively adsorbing
oxygen of the nucleotide may interact with the protonated and concentrating molecules in the primeval soup during
alumininol groups (AlOH2) through electrostatic forces, or chemical evolution. The results of this study on the adsorp-
it may establish hydrogen bonding with the AlOH groups tion of ribonucleotides on alumina lend support to this hy-
of alumina surfaces. At pH above 8.9 beyond ZPC, the sur- pothesis by demonstrating a strong degree of adsorption.
face of aluminum oxide becomes negatively charged due to This process may have protected these biomolecules from
the formation of AlO groups on its surface. There will be degradation and helped to preserve them for further poly-
repulsion between AlO and the negatively charged oxygen merization reactions.
atoms of nucleotides. So the adsorption is extremely low
(1–5%), as shown in Table 3. Abbreviations
The nature of the interaction between ribonucleotides and
alumina has been studied by means of infrared absorption. O.D., optical density; ZPC, zero point charge.
The infrared spectra of adenosine monophosphate, acidic
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