Raffaele Saladino

A possible prebiotic synthesis of purine, adenine, cytosine, and 4(3H)-pyrimidinone from formamide: implications for the origin of life.

The synthesis of prebiotic molecules is a major problem in chemical evolution as well as in any origin-of-life theory. We report here a plausible new prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide under catalytic conditions. In the presence of CaCO(3) and different inorganic oxides, namely silica, alumine, kaolin, and zeolite (Y type), neat formamide undergoes the formation of purine, adenine, cytosine, and 4(3H)-pyrimidinone, from acceptable to good yields. The role of catalysts showed to be not limited to the improvement of the yield but it is also relevant in providing a high selectivity in the products distribution.

One-Pot TiO2-Catalyzed Synthesis of Nucleic Bases and Acyclonucleosides from Formamide: Implications for the Origin of Life

A novel one‐pot TiO2‐catalyzed synthesis of nucleobases and acyclonucleosides from formamide is reported. Since formamide can be formed under prebiotic conditions, these reactions have implications for the origin of life. While a number of purine derivatives have been found as products of non‐TiO2‐catalyzed reactions, important compounds that would not otherwise occur (namely, thymine, 5hydroxymethyluracil, and acyclonucleosides) are formed in acceptable yields by TiO2‐catalyzed reactions. Moreover, TiO2 selectively affects the rates of degradation of nucleobases, as single units and when embedded in polynucleotides.

Selective oxidation of phenol and anisole derivatives to quinones with hydrogen peroxide and polymer-supported methylrhenium trioxide systems

Abstract A convenient and efficient application of heterogeneous poly(4-vinylpyridine)/methyl rhenium trioxide (PVP/MTO) systems for the selective oxidation of substituted phenol and anisole derivatives to benzoquinones is described. Environment friendly, easily available, and low cost H 2 O 2 was used as the oxygen atom donor. All catalysts were stable systems for at least five recycling experiments. In the oxidation of some natural phenols such as cardanol derivatives higher conversion and yields of benzoquinones were observed with respect to MTO in homogeneous phase suggesting a support-mediated molecular recognition process based on hydrogen-bonding interactions.

Advances in the Prebiotic Synthesis of Nucleic Acids Bases: Implications for the Origin of Life

Prebiotic chemistry plays a central role in the investigation of the possible scenarios of the early chemical environments. Its goal is to shed light on the events involved in the synthesis of initial biomolecules and on the self-organization processes that led the last common ancestor. Even though a well defined scenario for the physico-chemical conditions on the primitive Earth is not available, one can assume that a synthetic pathway, in order to be considered prebiotic, should use the simplest chemicals and the most common conditions present at that time. Low molecular weight molecules such as hydrogen cyanide and formaldehyde, easily formed from the primitive atmosphere by ultraviolet light, heat or electric discharge as energy sources, have been considered as prebiotic precursors. Here we focus on the attempts to identify the prebiotic events originating purine and pirimidine nucleic acids bases, the necessary components for the assembling of nucleosides, nucleotides and oligonucleotides. © 2004 Bentham Science Publishers Ltd.

Synthesis and Degradation of Nucleobases and Nucleic Acids by Formamide in the Presence of Montmorillonites

We describe the role of formamide, a product of the hydrolysis of hydrogen cyanide, as precursor of several components of nucleic acids under prebiotic conditions. When formamide is heated in the presence of montmorillonites, the efficient one‐pot synthesis of purine, adenine, cytosine, and uracil is obtained. Along with these nucleobases, several components of the inosine pathway are obtained: 5‐aminoimidazole‐4‐carboxamide, 5‐formamidoimidazole‐4‐carboxamide and hypoxanthine. This almost complete catalogue of nucleic acid precursors is accompanied by N9‐formylpurine, which, containing a masked glycosidic bond in its formyl moiety, is a plausible precursor of purine acyclonucleosides. In addition, montmorillonites differentially affect the rate of degradation of nucleobases when embedded in 2′‐deoxyoligonucleotides; namely, montmorillonites protect adenine and guanine from the degradative action of formamide, while thymine degradation is enhanced. The oligonucleotide backbone reactivity to formamide is also affected; this shows that the interaction with montmorillonites modifies the rate of abstraction of the Hα and Hβ protons on the sugar moieties.

Meteorite-catalyzed syntheses of nucleosides and of other prebiotic compounds from formamide under proton irradiation

Significance Modern research on the origin of life started with Urey–Miller’s 1953 report on the spontaneous formation of amino acids upon application of electric discharge on a model of the pristine Earth atmosphere. Formamide provides a chemically sound starting material for the syntheses of prebiotic compounds; its role in prebiotics is becoming recognized. Kiloparsecs-wide clouds of formamide were observed in the interstellar space. The energy sources for the syntheses explored so far were largely thermal, and the catalysts used were mostly terrestrial. In the presence of meteorites and with high-energy protons, we observe the production of unprecedented panels of nucleobases, sugars, and, most notably, nucleosides. Carboxylic acids and amino acids complete the recipe. These findings extend prebiotic plausible scenarios well beyond our planet. Liquid formamide has been irradiated by high-energy proton beams in the presence of powdered meteorites, and the products of the catalyzed resulting syntheses were analyzed by mass spectrometry. Relative to the controls (no radiation, or no formamide, or no catalyst), an extremely rich, variegate, and prebiotically relevant panel of compounds was observed. The meteorites tested were representative of the four major classes: iron, stony iron, chondrites, and achondrites. The products obtained were amino acids, carboxylic acids, nucleobases, sugars, and, most notably, four nucleosides: cytidine, uridine, adenosine, and thymidine. In accordance with theoretical studies, the detection of HCN oligomers suggests the occurrence of mechanisms based on the generation of radical cyanide species (CN·) for the synthesis of nucleobases. Given that many of the compounds obtained are key components of extant organisms, these observations contribute to outline plausible exogenous high-energy–based prebiotic scenarios and their possible boundary conditions, as discussed.

Synthesis and degradation of nucleic acid components by formamide and iron sulfur minerals

We describe the one-pot synthesis of a large panel of nucleic bases and related compounds from formamide in the presence of iron sulfur and iron-copper sulfur minerals as catalysts. The major products observed are purine, 1H-pyrimidinone, isocytosine, adenine, 2-aminopurine, carbodiimide, urea, and oxalic acid. Isocytosine and 2-aminopurine may recognize natural nucleobases by Watson-Crick and reverse Watson-Crick interactions, thus suggesting novel scenarios for the origin of primordial nucleic acids. Since the major problem in the origin of informational polymers is the instability of their precursors, we also investigate the effects of iron sulfur and iron-copper sulfur minerals on the stability of ribooligonucleotides in formamide and in water. All of the iron sulfur and iron-copper sulfur minerals stimulated degradation of RNA. The relevance of these findings with respect to the origin of informational polymers is discussed.

Conversion of naringenin and hesperetin by heterogeneous catalytic Baeyer-Villiger reaction into lactones exhibiting apoptotic activity

Naringenin and hesperetin were converted into the corresponding lactones by hydrogen peroxide activated by poly(4-vinylpiridine)-supported methyltrioxorhenium in t-butanol, an environmentally friendly catalytic system. The products showed a marked apoptotic activity in the genetic tests.

From formamide to RNA: the roles of formamide and water in the evolution of chemical information

In pursuing the origin of informational polymers, we followed the assumption that their spontaneous formation could only have occurred: (i) if all the components were present at the same site and in the same reaction, and (ii) if the thermodynamics of the processes involved favored a polymerized over a monomeric state of the precursors. A plausible scenario satisfying both assumptions is provided.

Selective epoxidation of monoterpenes with H2O2 and polymer-supported methylrheniumtrioxide systems

Abstract A convenient and efficient synthesis of monoterpene epoxides by application of heterogeneous poly(4-vinylpyridine)/methyl rhenium trioxide (PVP/MTO) and polystyrene/methyl rhenium trioxide (PS/MTO) systems is described. Even highly sensitive terpenic epoxides were obtained in excellent yield. Environment friendly, easily available, and low cost H 2 O 2 was used as oxidant. Catalysts were stable systems for at least five recycling experiments.