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Plausible prebiotic synthesis of aldopentoses from simple substrates, and formaldehyde

Article in Paleontological Journal · December 2013 DOI: 10.1134/S0031030113090062

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Irina Delidovich Oxana Taran RWTH Aachen University Boreskov Institute of Catalysis

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Valentin N Parmon Boreskov Institute of Catalysis

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Plausible Prebiotic Synthesis of Aldopentoses from Simple Substrates, Glycolaldehyde and Formaldehyde I. V. Delidovicha, O. P. Taranb, and V. N. Parmonc aBoreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, pr. akademika Lavrent’eva 5, Novosibirsk, 630090 Russia bNovosibirsk State Technical University, pr. K. Marksa, 20, Novosibirsk, 630073 Russia cNovosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia email: [email protected] Received February 15, 2012

Abstract—Possible ways of abiotic catalytic synthesis of biologically significant aldopentoses (, , , lyxose) from elementary substrates, i.e., formaldehyde (FA) and glycolaldehyde (GA) in aqueous solutions are discussed. Conditions in which the process of synthesis of yields up to 65% relative to the initial concentration of GA: homogeneous borate catalyst NaOH + H3BO3, pH 9, [GA]0 5 mM, [FA]0 50–100 mM have been found.

Keywords: prebiotic synthesis, aldopentoses, formaldehyde, borates, minerals DOI: 10.1134/S0031030113090062

INTRODUCTION et al., 2004) as a result of polymerization, dehydra The question of reaction conditions, in which bio tion, and destruction of . The low selec logically significant organic compounds (amino acids, tivity of this process casts doubt on the possibility that , nucleotides, etc.) could have selectively been it could have yielded biologically significant carbohy synthesized from elementary substrates at prebiotic drates in sufficient concentration for further chemical developmental stages of the biosphere, is widely dis reactions, such as synthesis of ATP, nucleic acids, cussed. Terrestrial ponds, thermal springs, space dust, , etc. comets, and even protoplanet circumstellar disk were As was previously shown, the selectivity of synthe proposed among possible objects that could have been sis of increases as the reaction “reactors” for prebiotic synthesis. Therefore, the study occurs in alkalescent medium and in the absence of of chemical transformations of elementary com Ca2+ ions (Simonov, 2007). As a result of condensation pounds, yielding biologically significant substances, of FA with lower monosaccharides, i.e., glycolic (GA) enables the revelation of conditions, in which this syn and glyceric (GCA) , and thesis provides a rather large yield and, hence, supple (DHA), the formation of and 3pentulose mentary arguments for certain models of prebiotic with the total yield ca. 75% was observed (Delidovich chemical evolution. et al., 2009; Simonov et al., 2007a, 2007b). It has been generally accepted for a long time that Monosaccharides of the aldopentose class (ribose, the most probable way of the synthesis of carbohy xylose, arabinose, lyxose) are stereoisomers differing drates from the simplest C1 substrate is the formose in spatial arrangement of hydroxyl and reaction of condensation of formaldehyde (FA) in the groups. In modern biochemistry, aldopentoses play an important role, being the building blocks of polysac presence of Ca(OH)2 to give sugars. The presence of FA in prebiotic conditions seems rather probable; the charides, glycosides, natural gums, and slime; ribose, lowtemperature interaction of amorphous which is included in ATP and RNA, is of particular with water results in the formation of hydroxymethyl importance. ene, isomerization of which produces FA (Ahmed In the present study, the possibility of synthesis of et al., 1983). However, a distinctive feature of the clas aldopentoses in a high yield in abiogenic conditions by sical formose reaction is simultaneous synthesis of sev catalytic condensation of GA with FA is analyzed. The eral dozen products, including linear and branched reaction of GA and FA was investigated in the pres sugars, organic acids, and polyols (Medvedeva et al., ence of homogeneous (phosphates, borates) and het 1983; Partridge et al., 1972). In addition, the reaction erogeneous (montmorillonites, apatite) catalysts, a mixture rapidly becomes yellowish brown (Riccardo sufficient amount of which could have been present on

1093 1094 DELIDOVICH et al.

Probable structures of byproducts, branched CHO monosaccharides

HO C CHOH CHOH CH2OH CH OH 2 CHO +FA CHOH CHO CHO +GA CHOH HO C CH2OH HO C CHOH CH2OH CHOH CH2OH CH2OH Pathway (1) CH2OH +FA CH2OH Aldopentoses CH OH +GCA CH2OH 2 +FA CHOH +GA CHO CH2OH CHOH CH OH GA CHO 2 C O C O C O +FA +FA GCA Pathway (2) CHOH CHOH Pathway (3) CH OH +Ga 2 CH2OH CH2OH DHA Erythrulose 3pentulose CHO CHOH CHOH

CH2OH Aldotetroses

Fig. 1. Pathways of synthesis of sugars from GA and FA in the presence of the basic catalysts. the prebiotic Earth. Note that the simplest lower (Kurgan deposits, 64% of humidity), and montmoril GA was recorded even in the inter lonite NaM (Azerbaijan, 85% of humidity). stellar space (Hollis et al., 2004); in terrestrial prebi otic conditions, it could have been formed as a result The values of pH in the reaction mixture were mea of a number of processes (Miller and Urey, 1959), for sured by pHmeter/ionomer Anion4101 (Infaspak example, photochemical condensation of FA in water Analit, Russia). During the experiment, reaction mix solutions (Pestunova et al., 2005). ture was sampled periodically to determine the con centrations of FA and carbohydrates by the highper formance liquid chromatography technique, with pre EXPERIMENTAL PART liminary derivatization of 2,4dinitrophenylhydrazine Experiments were performed in a deaerated ther (Cherstiouk et al., 2000), using a Milichrom A02 mostatically controlled (KRIOVT01 thermostat, chromatograph (Econova, Russia) with a ProntoSIL Russia) glass reactor, where 70 mL of solution of phos 1205C18 AQ column (75*2 mM) and a UV detector. phate or borate catalyst or water (if minerals were used as heterogeneous catalysts) were placed. Then, 21 mg of GA were solved (the initial concentration was RESULTS AND DISCUSSION 5 mM) and an appropriate aliquot of 7.33 M solution of FA (the initial concentration was 2.5–250 mM) was Figure 1 shows three main pathways of chemical charged into the reactor. In experiments with hetero reactions, in which GA and FA could be involved. geneous catalysts, 200 mg of mineral (calculated on Pathway (1) produces desirable products, aldopen dry weight) were added to the reaction mixture. Reac toses; pathway (2) gives erythrulose and 3pentulose; tions in the presence of homogeneous and heteroge and pathway (3) results in condensation of GA into neous catalysts lasted 8 and 52 h, respectively. Phos aldotetroses. In addition, reactions of interaction phates (0.2 M Na2HPO4 + KH2PO4, pH = 7.0; 8.0; between GA, GCA, and FA yielding branched 9.0) and borates (0.13 M H3BO3 + NaOH, pH = 9.0) monosaccharides are possible. This work was aimed at were tested as homogeneous catalysts and heteroge the search for the conditions, in which the rate of reac neous catalysts (minerals) were represented by apatite tions of pathway (1) prevails over the rates of all other (Kola Peninsula, Apatit), montmorillonite NaM processes.

PALEONTOLOGICAL JOURNAL Vol. 47 No. 9 2013 PLAUSIBLE PREBIOTIC SYNTHESIS OF ALDOPENTOSES 1095

Products of Condensation of GA with FA (a) in the Presence of Different Catalysts Aldopentoses Aldotetroses Stoichiometric molar ratio of GA and FA in the 3Pentulose Erythrulose reactions of synthesis of aldopentoses (pathway 1) is Branched monosaccharides 2 : 1. However, preliminary results have shown that, 100 when the substrates interact in stoichiometric amounts, the rate of pathway (3) is considerably higher 80 than the rate of (1) (Fig. 2b), due to higher electrophi licity of GA in comparison with FA. In addition, it is 60 highly improbable that, in prebiotic conditions, the concentration of GA was higher than that of FA 40 because of high reactivity of GA. Therefore, the study Yield, % of the effect of the catalyst nature on the composition 20 of products was performed in conditions of the excess 0 of FA, with the molar ratio GA : FA = 1 : 5. The 1234567 dependence of the yield of reaction product on the Catalysts catalyst nature is shown in Fig. 2a. (b) In the presence of heterogeneous catalysts, the Aldopentoses Aldotetroses products accumulated at a slower rate than over homogeneous catalysts. The reaction rate over the Branched monosaccharides minerals was in line with the pH value arisen from the 100 presence of the minerals in the reaction mixture, i.e., 80 acceleration of the condensation in the row of mont morillonite (Kurgan deposits, pH 7.5–6.3) < mont 60 morillonite (Azerbaijan, pH 8.7–7.0) < apatite (pH 8.8–7.9) was observed. In the presence of all min 40 erals, the pH in the reaction medium gradually Yield, % decreased in the course of reaction. Over montmoril 20 lonites, aldotetroses and aldopentoses accumulated in 0 the reaction medium during the first 10–20 h of reac 2 : 1 1 : 5 1 : 10 1 : 20 1 : 50 tion; subsequently, the concentration of the products Ratio of concentrations GA : FA, mM : mM remained the same. In the presence of apatite, the maximum concentration of aldopentoses was Fig. 2. Distribution of the products formed in the course of observed in 20 hours after the beginning of the reac condensation of GA with FA in the presence of the basic tion; then, the concentration of the main products catalysts. Reaction conditions: (a) 60°C, [GA]0 = 5 mM, decreased. Simultaneously, the formation of branched [FA]0 = 25 mM, catalysts: (1) montmorillonite, Kurgan monosaccharides was observed. The yield of aldopen deposits; (2) montmorillonite, Azerbaijan; (3) apatite; toses over minerals was 5–15% relative to GA. 0.2M Na2HPO4 + KH2PO4: (4) pH 7, (5) pH 8, (6) pH 9; (7) 0.13 M H3BO3 + NaOH, pH 9; (b) 60°C, [GA]0 = In the presence of phosphate buffer Na2HPO4 + 5mM, [FA]0 = 2.25–250 mM, catalyst 0.13 M H3BO3 + NaOH, pH 9. KH2PO4, the conversion of GCA into DHA as a result of isomerization reached 50–80%; therefore, a signif icant part of the substrate was spent on pathway (2) and reached ca. 40% relative to GA. The difference in and the yield of aldopentoses was 5–30% relative to the composition of products in the presence of phos GA. The change in the initial pH of the reaction medium from 7.0 to 9.0 resulted in an increase in the phate and borate catalysts was probably caused by the rate of all reactions, including synthesis of byprod stabilization of the intermediate product of synthesis ucts, the branched monosaccharides. In the presence of aldopentoses, GCA due to interaction of these of phosphate catalysts, the reaction mixture became compounds with borate ion, which prevented its yellow in several hours after the beginning of the isomerization in DHA and promoted the target path experiment, which was evidence of dehydration of way (1). The synthesis of complexes of higher monosaccharides. According to the previously monosaccharides with borate ions also prevents fur obtained results (Delidovich et al., 2009), an increase ther transformations of aldopentose (Riccardo et al., in the molar ratio of the initial concentration of the 2004). Riccardo and coauthors proposed that borate substrates GA : FA from 1 : 5 to 1 : 20 results in reac ions could have played an important role in stabiliza tion following pathway (2) to give erythrulose and 3 tion of sugars in prebiotic conditions. Our studies have pentulose. shown that borate anions can not only stabilize The maximum yield of aldopentoses was observed monosaccharides, but also catalyze their formation in the presence of the borate catalyst H3BO3 + NaOH from simple substrates. Since borates constitute some

PALEONTOLOGICAL JOURNAL Vol. 47 No. 9 2013 1096 DELIDOVICH et al. minerals and clays (serpentine, montmorillonite, etc.) of Sciences “Origin of Biosphere and Evolution of (Ivanov, 1996) and are present in thermal springs in Geobiological Systems.” high concentrations (Vulkanizm …, 1974), this sce nario for the appearance of biologically important pentoses in significant quantity seems rather probable. REFERENCES Ahmed, S.N., McKee, M.L., and Shevlin, P.B., An Exper imental and ab initio Study of the Addition of Atomic Car Effect of Molar Ratios of Substrates on Condensation bon to Water, J. Am. Chem. Soc., 1983, vol. 105, pp. 3942– of GA with FA in the Presence of Borate Catalyst 3947. 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Nauk, 2007. tive to glycolaldehyde) is observed in the presence of Simonov, A.N., Matvienko, L.G., Pestunova, O.P., Par borate catalyst, with the initial concentrations of mon, V.N., Komandrova, N.A., Denisenko, V.A., and formaldehyde and glycolaldehyde of 50–100 mM and Vas’kovskii, V.E., Selective Synthesis of Erythrulose and 5 mM, respectively. Perhaps, the high selectivity of 3Pentulose from Formaldehyde and Dihydroxyacetone, Catalyzed by Phosphates in a Neutral Aqueous Medium, borate catalyst results from the stabilization of the Kinet. Katal., 2007, vol. 4, no. 4, pp. 586–592. intermediate product (glyceraldehyde) and target pen toses in the stable complex with borate, which prevents Simonov, A.N., Pestunova, O.P., Matvienko, L.G., Snytni kov, V.N., Snytnikova, O.A., Tsentalovich, Yu.P., and Par their further transformation into branched sugars and mon, V.N., Possible Prebiotic Synthesis of Monosaccha other byproducts. rides from Formaldehyde in Presence of Phosphates, Adv. Space Res., 2007, vol. 40, no. 11, pp. 1634–1640. Vulkanizm, gidrotermal’nyi protsess i rudoobrazovanie (Vol ACKNOWLEDGMENTS canism, Hydrothermal Process, and Ore Formation), We are grateful to S.A. Yashnik for providing mont Naboko, S.I., Eds., Moscow: Nedra, 1974. morillonite samples. The study was supported by the Program for Basic Research of the Russian Academy Translated by G. Rautian

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