PubMed Health⌕ Search

Biomedical subjects

R Navarro-González

Publications and source records attributed to R Navarro-González.

13 recordsLinked to original sources

A possible nitrogen crisis for Archaean life due to reduced nitrogen fixation by lightning.

Nitrogen is an essential element for life and is often the limiting nutrient for terrestrial ecosystems. As most nitrogen is locked in the kinetically stable form, N2, in the Earth's atmosphere, processes that can fix N2 into biologically available forms-such as nitrate and ammonia-control the supply of nitrogen for organisms. On the early Earth, nitrogen is thought to have been fixed abiotically, as nitric oxide formed during lightning discharge. The advent of biological nitrogen fixation suggests that at some point the demand for fixed nitrogen exceeded the supply from abiotic sources, but the timing and causes of the onset of biological nitrogen fixation remain unclear. Here we report an experimental simulation of nitrogen fixation by lightning over a range of Hadean (4.5-3.8 Gyr ago) and Archaean (3.8-2.5 Gyr ago) atmospheric compositions, from predominantly carbon dioxide to predominantly dinitrogen (but always without oxygen). We infer that, as atmospheric CO2 decreased over the Archaean period, the production of nitric oxide from lightning discharge decreased by two orders of magnitude until about 2.2 Gyr. After this time, the rise in oxygen (or methane) concentrations probably initiated other abiotic sources of nitrogen. Although the temporary reduction in nitric oxide production may have lasted for only 100 Myr or less, this was potentially long enough to cause an ecological crisis that triggered the development of biological nitrogen fixation.

Atmosphere↗

PM3, AM1, MNDO and MINDO3 semi-empirical IR spectra simulations for compounds of interest for Titan's chemistry: diazomethane, methyl azide, methyl isocyanide, diacetylene and triacetylene.

Four semi-empirical methods (PM3, AM1, MNDO and MINDO3) have been tested to find the best auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) identification of five compounds of interest for Titan's atmospheric chemistry as test compounds: diacetylene, triacetylene, diazomethane, methyl azide, methyl isocyanide. Of the four methods, MINDO3 can be considered as the most appropriate method to facilitate the identification of such and similar compounds, since (1) the simulated IR spectra best match the experimental spectra for four compounds of five studied; and (2) MINDO3 provides the best linearity between the calculated and experimental frequencies (correlation coefficient of 0.995; a scaling factor of 0.84 can be applied to afford better correspondence between the calculated and experimental wavenumbers). None of the semi-empirical methods tested is able to predict (even approximately) infrared band intensities, and therefore a spectral intensity pattern.

Acetylene↗

PM3, AM1, MINDO3 semi-empirical IR spectra simulations for some nitriles of interest for Titan's chemistry.

A set of the semi-empirical methods (PM3, AM1, MNDO and MINDO3) has been tested to find the best auxiliary tool for the identification of nitriles by gas chromatography/Fourier transform IR spectroscopy/mass spectrometry, considering five nitriles of interest for Titan's chemistry as test compounds: acetonitrile, acrylonitrile, cyanoacetylene, 2-butynenitrile and dicyanoacetylene. Of the four semi-empirical methods, MNDO can be considered as the most advantageous auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) identification of nitriles of interest for Titan's atmospheric chemistry, since (1) the simulated IR spectra best match the experimental (in some cases AM1 gives comparable results); (2) it provides the best linearity between the calculated and experimental frequencies (correlation coefficient of 0.990); a scaling factor of 0.90 can be applied to afford better correspondence between the calculated and experimental wavenumbers. At the same time, none of the methods is able to predict infrared intensities and a spectral intensity pattern.

Computer Simulation↗

Chemical studies on the possible existence of life on Mars.

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.

Aluminum Silicates↗

Role of trace metal ions in chemical evolution. The case of free-radical reactions.

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.

Acetic Acid↗

An extended cellular space method for simulating autocatalytic oligonucleotides.

Self-replicating nucleotides and other self-replicating molecules are an active area of study today by organic chemists. Such studies are important for improving our understanding of the origins of life. Computational studies of self-replicating molecules could increase our insight into their properties, but existing computational techniques have been limited in their usefulness for such reactions (numerical simulation of differential equations requires reaction rate constants that are difficult to obtain, cellular automata models are too restrictive for modeling molecular movements and bindings, etc.). We have thus developed an efficient modified cellular automata method that supports the study of self-replicating oligonucleotides. We explain this method and illustrate its use with a specific self-replicating (autocatalytic) deoxyribohexanucleotide.

Algorithms↗

Computational study of radiation chemical processing in comet nuclei.

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.

Cosmic Radiation↗

Chemical studies on the existence of extraterrestrial life.

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.

Amino Acids↗

Radiolysis of aqueous solutions of acetic acid in the presence of Na-montmorillonite.

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.

Acetates↗

The gamma-irradiation of aqueous hydrogen cyanide in the presence of ferrocyanide or ferricyanide: implications to prebiotic chemistry.

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.

Ammonia↗

A quantitative assay of biologically important compounds in simulated primitive Earth experiments.

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.

Aldehydes↗