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Although there is no direct evidence yet for the existence of life on Mars, it is reasonable to conclude that the emergence of life on Earth, which appears to have been controlled by universal laws of physics and chemistry, may have been repeated elsewhere in the universe. The dual approach of synthesis and analysis in our experimental studies has provided ample evidence in support of this hypothesis.

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We have studied the effect of iron in the free-radical oligomerization of hydrogen cyanide and acetic acid, and found that iron(II) and iron(III) readily reduces or oxidizes free radicals, respectively. The transient species produced by these reactions do not induce a chain oligomerization process and, therefore, they protect the solute molecules from degradation. Analysis of the available kinetic data for the reactions of a variety of transition metal ions with free radicals indicate that transition metal ions behave similarly to iron. Since Fe, Zn and Mo are essential to all living organisms, and there seems to be no apparent difference in chemical reactivity among transition metal ions towards free radicals, we suggest that these metal ions probably protected the biomolecules from degradation induced by free-radical reactions in the later stages of chemical evolution.

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A study of the association of homocodonic amino acids and selected heterocodonic amino acids with selected nucleotides in aqueous solution was undertaken to examine a possible physical basis for the origin of codon assignments. These interactions were studied using 1H nuclear magnetic resonance spectroscopy (NMR). Association constants for the various interactions were determined by fitting the changes in the chemical shifts of the anomeric and ring protons of the nucleoside moieties as a function of amino acid concentration to an isotherm which described the binding interaction. The strongest association of all homocodonic amino acids were with their respective anticodonic nucleotide sequences. The strength of association was seen to increase with increase in the chain length of the anticodonic nucleotide. The association of these amino acids with different phosphate esters of nucleotides suggests that a definite isomeric structure is required for association with a specified amino acid; the 5'-mononucleotides and (3'-5')-linked dinucleotides are the favored geometries for strong associations. Use of heterocodonic amino acids and nonprotein amino acids supports these findings. We conclude that there is at least a physicochemical, anticodonic contribution to the origin of the genetic code.

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Cometary nuclei have been exposed to high levels of ionizing radiation since their formation. We present here some results of a computer model calculation of the effect of ionizing radiation on cometary material. The external (cosmic rays) and internal (embedded radionuclides) contributions in the processing of cometary nuclei are considered. As a first approximation we have used the available kinetic data of the liquid water system to model the radiation effects in a frozen cometary environment. Our [correction of out] data suggest that massive radiation chemical processing due to cosmic rays may have taken place only in the outer layers of comets. The internal contribution of radionuclides to the radiation processing of comet cores seems to be modest. Therefore, comets could be carriers of intact homochiral biomolecules.

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Although the search for extraterrestrial intelligence has not produced any direct evidence of extraterrestrial life, the emergence of life on Earth, which appears to be controlled by universal laws of physics and chemistry, must have been repeated elsewhere in the universe. The experimental approaches in our laboratory to understand the origin of life on the Earth are summarized in an attempt to obtain a better insight into the chemical basis of extraterrestrial life.

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We have synthesized and studied the properties of phosphoanhydrides of alanine with guanosine monophosphate, uridine monophosphate, and adenosine monophosphate. This series of compounds allowed us to investigate the specificity of peptide bound formation in a reaction that could have taken place on the prebiotic earth. We asked whether the intrinsic reactivity of the amino acids, the nature of the nucleotide in the anhydride, or the complementary polynucleotide template influences the specificity of the peptide synthesis reaction. We observed that the differential reactivity of the amino acids results in nearest-neighbor preferences during the peptide synthesis, whereas the nature of the nucleotides and the presence of complementary polynucleotides had no influence on the specificity. These results suggest that some peptides would have been more abundant than others on the prebiotic earth and have implications for the study of the origins of the genetic code and protein synthesis.

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The gamma-irradiation of 0.8 mol dm-3 aqueous, oxygen-free acetic acid solutions was investigated in the presence or absence of Na-montmorillonite. H2, CH4, CO, CO2, and several polycarboxylic acids were formed in all systems. The primary characteristics observed in the latter system were: (1) Higher yield of the decomposition of acetic acid; (2) Lower yield of the formation of polycarboxylic acids; (3) No effect on the formation of methane; (4) Higher yield of the formation of carbon dioxide; and (5) The reduction of Fe3+ in the octahedral sites of Na-montmorillonite. A possible reaction scheme was proposed to account for the observed changes. The results are important in understanding heterogeneous processes in radiation catalysis and might be significant to prebiotic chemistry.

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A CH4-N2-H2OV gas mixture was subjected to a high voltage (20 kV), high frequency (0.3 MHz) electric discharge. The energy input in the electric discharge was varied from 0.016 to 3.048 MJ mol-1. The chemical yields (G), expressed as the number of molecules formed or destroyed per 100 eV of energy input were calculated for several products. The G values calculated at the lowest energy input were (-CH4) = 6.48; (-N2) = 2.51; (C2H2) = 1.16; (HCN) = 0.215; (CH3CHO) = 0.115; (CH3CH2CHO) = 0.00161; (CH3(CH2)2CHO) = 0.0165; ((CH2CO2H)2) = 0.0000339; (CH4 --> Solid material) = 0.196; (N2 --> Solid material) = 0.00355. This is the first report in prebiotic studies in which the G values of various products in electric discharge experiments are determined. This type of study is needed in order to get a better insight into the relative role of electric discharges on the primitive Earth.

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The gamma-irradiation of 0.1 M, O2-free, aqueous HCN was studied in the presence of ferrocyanide or ferricyanide in the concentration range 10(-3) - 10(-5) M. This study was carried out in order to get an insight into the possible role that cyanocomplexes of iron may have played in promoting prebiotic syntheses via the free-radical oligomerization of HCN. It was found that ferrocyanide or ferricyanide have no effect on the irradiation of 0.1 M HCN solutions at concentrations < or = 10(-4) M. At high concentrations, 10(-3) M, they lead to a marked decrease in the conversion of HCN. There was no significant difference due to the oxidation state of iron used, particularly at high doses > or = 100 kGy.

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Modern astronomy suggests that planets are plentiful in the Universe and that the conditions suitable for life are commonplace. Advances in biochemistry have pointed out the unity of the biosphere and lead to the belief that all life had a common chemical origin. Laboratory experiments indicate that almost all the building blocks of life can be synthesized under simulated primitive Earth conditions. The analysis of meteorites and the study of the interstellar medium indicate that molecules of biological interest are commonplace in the Universe, thus leading to the conclusion that the evolutionary process which has taken place on Earth may have also occurred elsewhere in the cosmos leading to extraterrestrial civilisations.

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This bibliography is the seventeenth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci. 2(1970), 225-295; 3(1972), 293-304; 4(1973), 309-329 and in Origins of Life 5(1974), 505-527; 6(1975), 285-300; 7(1976), 75-85; 8(1977), 59-66; 9(1978), 67-74; 10(1980), 69-87; 10(1980), 379-404; 11(1981), 273-288; 12(1982), 93-118; 13(1983), 61-80; 15(1984), 55-69; 17(1987), 171-184; 17(1987), 185-206.

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In order to examine the effect of a defined enantiomeric sequence on protein structure, the all-D model ribonuclease S-peptide, H-Ala-Glu-Ala4-Lys-Phe-Ala-Arg-Ala-His-Met-Ala2-OH, has been synthesized by the solid phase method. The all-L peptide has been synthesized previously and shown to possess 36% of ribonuclease S activity when added to ribonuclease S-protein (Komoriya, A. & Chaiken, I.M. (1982) J. Biol. Chem 257, 2599-2604). The synthetic D-peptide was purified by gel filtration and semipreparative reverse phase HPLC. Amino acid composition of the synthetic peptide was in agreement with theory and gas chromatographic analysis showed that no significant racemization had occurred during synthesis. Circular dichroism (CD) studies of the D-peptide showed a peak of positive ellipticity in the 220-230 nm region, whereas a negative ellipticity peak for the L-peptide was observed. The effects of temperature and trifluoroethanol on the far-ultraviolet CD spectra of D- and L-peptides were similar but of opposite sign, confirming the expectation that the D-peptide has the propensity to form an alpha-helical structure which is enantiomeric with respect to that formed by the L-peptide. In the presence of S-protein, the L-peptide showed hydrolytic activity against the substrate cytidine-2':3'-monophosphate, whereas the D-peptide was inactive. Addition of the D-peptide to mixtures of L-peptide and S-protein did not lead to inhibition of enzymatic activity. These results indicate lack of binding of D-peptide to S-protein to produce either an active or inactive species.

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Research on trace elements in chemical evolution is reviewed from three points of view. They are: the origin of the essentiality of trace elements in present biological systems; the possible roles of trace elements in chemical evolution; and the origin of enzymatic activity with metal ions, i.e., the origin of metalloenzymes.

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Electric discharge experiments have been performed in a plausible primitive earth atmosphere consisting of methane, nitrogen, and water over an aqueous phase of an ammonia-ammonium buffer solution. In some experiments, ions of metal elements, calcium, magnesium, zinc, iron and molybdenum were introduced. Gas phase products and amino acids in the liquid phase were analyzed by gas chromatography. With trace metal ions, less organic compounds in the gas phase and larger amounts of amino acids were obtained than without them. The results have shown the possible importance of trace elements in chemical evolution and the origin of life on the earth.

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The bibliography is the thirteenth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci. 2(1970), 225-295; 3(1972), 293-304; 4(1973), 309-329 and in Origins of Life 5(1974), 505-527; 6(1975), 285-300; 7(1976); 75-85; 8(1977), 59-66; 9(1978), 67-74; 10(1980), 69-87; 10(1980), 379-404; 11(1981), 273-288; 12(1982), 93-118; 13(1983), 61-80.

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