SEARCH · PubMed Health

Results for “Evolution, Chemical”

Explore indexed PubMed citations for clinical trials, systematic reviews and public health research. Read source abstracts and follow each citation to its original PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 649 records · Page 36Linked to original sources

PubMed1989

Pre-biotic organic matter from comets and asteroids.

Several authors have suggested that comets or carbonaceous asteroids contributed large amounts of organic matter to the primitive Earth, and thus possibly played a vital role in the origin of life. But organic matter cannot survive the extremely high temperatures (>10(4) K) reached on impact, which atomize the projectile and break all chemical bonds. Only fragments small enough to be gently decelerated by the atmosphere--principally meteors of 10(-12)-10(-6) g--can deliver their organic matter intact. The amount of such 'soft-landed' organic carbon can be estimated from data for the infall rate of meteoritic matter. At present rates, only approximately 0.006 g cm-2 intact organic carbon would accumulate in 10(8) yr, but at the higher rates of approximately 4 x 10(9) yr ago, about 20 g cm-2 may have accumulated in the few hundred million years between the last cataclysmic impact and the beginning of life. It may have included some biologically important compounds that did not form by abiotic synthesis on Earth.

Atmosphere↗

PubMed1997

The first living systems: a bioenergetic perspective.

The first systems of molecules having the properties of the living state presumably self-assembled from a mixture of organic compounds available on the prebiotic Earth. To carry out the polymer synthesis characteristic of all forms of life, such systems would require one or more sources of energy to activate monomers to be incorporated into polymers. Possible sources of energy for this process include heat, light energy, chemical energy, and ionic potentials across membranes. These energy sources are explored here, with a particular focus on mechanisms by which self-assembled molecular aggregates could capture the energy and use it to form chemical bonds in polymers. Based on available evidence, a reasonable conjecture is that membranous vesicles were present on the prebiotic Earth and that systems of replicating and catalytic macromolecules could become encapsulated in the vesicles. In the laboratory, this can be modeled by encapsulated polymerases prepared as liposomes. By an appropriate choice of lipids, the permeability properties of the liposomes can be adjusted so that ionic substrates permeate at a sufficient rate to provide a source of monomers for the enzymes, with the result that nucleic acids accumulate in the vesicles. Despite this progress, there is still no clear mechanism by which the free energy of light, ion gradients, or redox potential can be coupled to polymer bond formation in a protocellular structure.

Energy Metabolism↗

PubMed2001

Chemical differentiation in regions of massive star formation.

We have reexamined the origin of the apparent differentiation between nitrogen-bearing molecules and complex oxygen-bearing molecules that is observed in hot molecular cores associated with massive protostars. Observations show that methanol is an ubiquitous and abundant component of protostellar ices. Recent observations suggest that ammonia may constitute an appreciable fraction of the ices toward some sources. In contrast to previous theories that suggested that N/O differentiation was caused by an anticorrelation between methanol and ammonia in the precursor grain mantles, we show that the presence of ammonia in mantles and the core temperature are key quantities in determining N/O differentiation. Calculations are presented which show that when large amounts of ammonia are evaporated alkyl cation transfer reactions are suppressed and the abundances of complex O-bearing organic molecules greatly reduced. Cooler cores (100 K) eventually evolve to an oxygen-rich chemical state similar to that attained when no ammonia was injected, but on a timescale that is an order of magnitude longer (~10(5) yr). Hotter cores (300 K) never evolve an O-rich chemistry unless ammonia is almost absent from the mantles. In this latter case, a complex O-rich chemistry develops on a timescale of ~10(4) yr, as in previous models, but disappears in about 2 x 10(5) yr, after which time the core is rich in NH3, HCN, and other N-bearing molecules. There are thus two ways in which N-rich cores can occur. We briefly discuss the implications for the determination of hot-core ages and for explaining N/O differentiation in several well-studied sources.

Ammonia↗

PubMed1996

A review of conditions affecting the radiolysis due to 40K on nucleic acid bases and their derivatives adsorbed on clay minerals: implications in prebiotic chemistry.

This paper describes the possible effects of ionizing radiation arising from long-lived soluble radionuclides within clays, in particular 40K, at the epoch of the emergence of life on Earth. The free dispersion of soluble radionuclides constitutes an effective in situ irradiation mechanism that might have acted upon adsorbed nucleic bases and their derivatives on clays, inducing chemical changes on these organic molecules. Several types of well documented reactions for radiolysis of nucleic acid bases and their derivatives are known, even at low doses (i.e., 0.1 Gy). For example, estimates with a dose rate calculated from 40K from deep sea clays at 3.8 Ga ago, indicates that over a period of 1000 years the amount of organic material transformated is 1.8 X 10(-7) moles/kg-clay. Although ionizing radiation may also induce synthetic reactions with prebiological interest, all in all these considerations indicate that nucleic acid bases and their derivatives adsorbed on clays were exposed for long periods to degradation conditions. Such situation promotes decomposition of organic molecules rather than protection of them and enhancement of farther polymerization, as it has been usually taken for granted.

Adsorption↗

PubMed2005

Catalytic activities of [GADV]-peptides. Formation and establishment of [GADV]-protein world for the emergence of life.

We have previously postulated a novel hypothesis for the origin of life, assuming that life on the earth originated from "[GADV]-protein world", not from the "RNA world" (see Ikehara's review, 2002). The [GADV]-protein world is constituted from peptides and proteins with random sequences of four amino acids (glycine [G], alanine [A], aspartic acid [D] and valine [V]), which accumulated by pseudo-replication of the [GADV]-proteins. To obtain evidence for the hypothesis, we produced [GADV]-peptides by repeated heat-drying of the amino acids for 30 cycles ([GADV]-P(30)) and examined whether the peptides have some catalytic activities or not. From the results, it was found that the [GADV]-P(30) can hydrolyze several kinds of chemical bonds in molecules, such as umbelliferyl-beta-D-galactoside, glycine-p-nitroanilide and bovine serum albumin. This suggests that [GADV]-P(30) could play an important role in the accumulation of [GADV]-proteins through pseudo-replication, leading to the emergence of life. We further show that [GADV]-octapaptides with random sequences, but containing no cyclic compounds as diketepiperazines, have catalytic activity, hydrolyzing peptide bonds in a natural protein, bovine serum albumin. The catalytic activity of the octapeptides was much higher than the [GADV]-P(30) produced through repeated heat-drying treatments. These results also support the [GADV]-protein-world hypothesis of the origin of life (see Ikehara's review, 2002). Possible steps for the emergence of life on the primitive earth are presented.

Alanine↗

PubMed2000

A replicator was not involved in the origin of life.

Many scientific theories of the origin of life suggest that life began with the spontaneous formation of a replicator (a self-copying organic polymer) within an unorganized chemical mixture, or "soup." A profound difficulty exists, however, with the idea of RNA, or any other replicator, at the start of life. Existing replicators can serve as templates for the synthesis of additional copies of themselves, but this device cannot be used for the preparation of the very first such molecule, which must arise spontaneously from an unorganized mixture. The formation of an information-bearing homopolymer through undirected chemical synthesis appears very improbable. The difficulties involved in such a synthesis are illustrated by considering the prospects for the assembly of a polypeptide of L-alpha-amino acids, based on the contents of the Murchison meteorite as an example of a mixture of abiotic origin. In that mixture, potential replicator components would be accompanied by a host of interfering substances, which include chain terminators (simple carboxylic acids and amines), branch-formers, D-amino acids, and many classes of substances for which incorporation would disrupt the necessary structural regularity of the replicator. Laboratory experiments dealing with the nonenzymatic synthesis of biopolymers have not addressed the specificity problem. The possibility that formation of the first replicator took place through a very improbable event cannot be excluded, but greater attention should be given to metabolism-first theories, which avoid this difficulty.

Biopolymers↗

PubMed1986

Chemical effects of large impacts on the Earth's primitive atmosphere.

Intense bombardment of the moon and terrestrial planets approximately 3.9-4.0 x 10(9) years ago could have caused the chemical reprocessing of the Earth's primitive atmosphere. In particular, the shock heating and rapid quenching caused by the impact of large bodies into the atmosphere could produce molecules such as HCN and H2CO4 which are important precursors for the abiotic synthesis of complex organic molecules. Here we model the production of HCN and H2CO by thermochemical equilibrium and chemical kinetic calculations of the composition of shocked air parcels for a wide range of temperatures, pressures and initial compositions. For atmospheres with C/O > or = 1, our results suggest that bolide impacts cause HCN volume mixing ratios of approximately 10(-3) to 10(-5) in the impact region and global average ratios of 10(-5) to 10(-12). The corresponding H2CO mixing ratios in the impact region are 10(-7) to 10(-9); no-global mixing can occur, however, as H2CO is rapidly destroyed or rained out of the atmosphere within days to hours. Rainout to the oceans of 3-15% of the HCN produced can provide approximately (3-14) x 10(11) mol HCN per year. This is somewhat larger than other predicted sources of HCN and H2CO on the primitive Earth.

Atmosphere↗

PubMed2006

Cometary impact and amino acid survival--chemical kinetics and thermochemistry.

The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9 degrees above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometary delivery of amino acids to early Earth is highly unlikely.

Amino Acids↗

PubMed1964

Organic constituents of carbonaceous chondrites.

From a brief discussion of forms of meteorite carbon it is concluded that almost all the carbon in the carbonaceous chondrites is present as organic matter. Attempts to extract and identify this organic matter are then reviewed. It is shown that only 25 per cent has been extracted and only about 5 per cent chemically characterized. Of this 5 per cent, most is a complex mixture of hydroxylated aromatic acids together with various hydrocarbons of the paraffin, naphthene and aromatic series. Small amounts of amino acids, sugars and fatty acids also are present. The possible chemical nature of the major fraction is discussed. It is suggested to be a mixture of high-molecular weight aromatic and hydrocarbon polymers. Possible sources of contamination of the meteorites are described and evidence indicating a general lack of organic contaminants is presented. It is concluded, that most of the organic constituents are indigenous to the meteorites and are extra terrestrial in origin. Synthetic processes for the compounds are mentioned and it is concluded that the organic material is probably of abiogenic origin. A brief review on studies of "organized elements" contained within the meteorites is presented. Difficulties of identification are discussed and photographs of some microstructures of several carbonaceous chondrites are presented. No final conclusion about the nature of these objects is possible, but some appear to be various indigenous organic and mineral structures, while others are terrestrial contaminants.

Amino Acids↗

PubMed2005

The formation of glycerol monodecanoate by a dehydration condensation reaction: increasing the chemical complexity of amphiphiles on the early Earth.

Dehydration/condensation reactions between organic molecules in the prebiotic environment increased the inventory and complexity of organic compounds available for self-assembly into primitive cellular organisms. As a model of such reactions and to demonstrate this principle, we have investigated the esterification reaction between glycerol and decanoic acid that forms glycerol monodecanoate (GMD). This amphiphile enhances robustness of self-assembled membranous structures of carboxylic acids to the potentially disruptive effects of pH, divalent cation binding and osmotic stress. Experimental variables included temperature, water activity and hydrolysis of the resulting ester product, providing insights into the environmental conditions that would favor the formation and stability of this more evolved amphiphile. At temperatures exceeding 50 degrees C, the ester product formed even in the presence of bulk water, suggesting that the reaction occurs at the liquid interface of the two reactants and that the products segregate in the two immiscible layers, thereby reducing hydrolytic back reactions. This implies that esterification reactions were likely to be common in the prebiotic environment as reactants underwent cycles of wetting and drying on rare early landmasses at elevated temperatures.

Chromatography, Thin Layer↗

PubMed1998

Carbonaceous micrometeorites from Antarctica.

Over 100 000 large interplanetary dust particles in the 50-500 micrometers size range have been recovered in clean conditions from approximately 600 tons of Antarctic melt ice water as both unmelted and partially melted/dehydrated micrometeorites and cosmic spherules. Flux measurements in both the Greenland and Antarctica ice sheets indicate that the micrometeorites deliver to the Earth's surface approximately 2000x more extraterrestrial material than brought by meteorites. Mineralogical and chemical studies of Antarctic micrometeorites indicate that they are only related to the relatively rare CM and CR carbonaceous chondrite groups, being mostly chondritic carbonaceous objects composed of highly unequilibrated assemblages of anhydrous and hydrous minerals. However, there are also marked differences between these two families of solar system objects, including higher C/O ratios and a very marked depletion of chondrules in micrometeorite matter; hence, they are "chondrites-without-chondrules." Thus, the parent meteoroids of micrometeorites represent a dominant and new population of solar system objects, probably formed in the outer solar system and delivered to the inner solar system by the most appropriate vehicles, comets. One of the major purposes of this paper is to discuss applications of micrometeorite studies that have been previously presented to exobiologists but deal with the synthesis of prebiotic molecules on the early Earth, and more recently, with the early history of the solar system.

Antarctic Regions↗

PubMed2001

Some observations on amino acid racemization under pyrolytic temperatures and inorganic oxide-catalyzed intermolecular condensation.

The problem of homochirality is of crucial importance for the origins of Life. While most laboratory studies are focused on the search of physical and chemical sources of handedness in the Universe, they reflect only one aspect of the problem: the origin of homochiral biomolecules. At the same time, any space environments where biomolecules are expected to form and where they have to pass through before the first primitive forms of Life emerge, include strong irradiation or/and high temperatures. This automatically implies the possibility of losing the optical activity, i.e. racemization. The simulation experiments performed by our group deal with the following two aspects of amino acid abiotic chemistry: (1) amino acid pyrolysis associated with their extraterrestrial delivery; and (2) peptide formation from amino acids catalyzed by inorganic oxides. According to our observations, the racemization phenomena are very common in the systems considered, not only under pyrolytic temperatures, but in some cases also under rather mild conditions (<100 degrees C). Our results put additional constraints on the environments where the chirality of biomolecules can be efficiently preserved.

Aluminum Oxide↗

PubMed1984

The chemical conditions on the parent body of the Murchison meteorite: some conclusions based on amino, hydroxy and dicarboxylic acids.

Amino and hydroxy acids have been identified in the Murchison meteorite. Their presence is consistent with a synthetic pathway involving aldehydes, hydrogen cyanide and ammonia in an aqueous environment (Strecker-cyanohydrin synthesis). From the various equilibrium and rate constants involved in this synthesis, four independent estimates of the ammonium ion concentrations on the parent body at the time of compound synthesis are obtained; all values are about 2 x 10(-3) M. Succinic acid and beta-alanine have also been detected in the Murchison meteorite. Their presence is consistent with a synthesis from acrylonitrile, hydrogen cyanide and ammonia. Using the equilibrium and rate constants for this synthetic pathway, and the succinic acid/beta-alanine ratio measured in the Murchison meteorite, an estimate of the hydrogen cyanide concentration of 10(-3) to 10(-2) M is obtained. Since hydrogen cyanide hydrolyzes relatively rapidly in an aqueous environment (t1/2 < 10(4) yrs) this high concentration implies a period of synthesis of organic compounds as short as 10(4) years on the Murchison meteorite parent body.

Acrylonitrile↗

PubMed1997

Characterization and divalent metal-ion dependence of in vitro selected deoxyribozymes which cleave DNA/RNA chimeric oligonucleotides.

By in vitro selection, a variety of catalytic DNA oligonucleotides were obtained which cleave chimeric oligonucleotides at a single ribonucleotide position embedded within a deoxyribonucleotide context in the presence or absence of divalent metal ions. After several cycles of selection/amplification in the absence and in the presence of low amounts of Mg2+ two different types of catalysts emerged: one type depended strongly on Mg2+ or other divalent metal ions, the other type performed cleavage reactions independently of Mg2+ in the presence of spermine. Experimental analysis of the secondary structure of some of the selected deoxyribozymes was carried out by chemical probing. The ribonucleotide in the selected catalysts is unpaired and presents the cleavage site to the attacking nucleophile. Our results suggest that the main selection criterion under metal-free conditions was a favourable arrangement of the attacking nucleophile and the phosphate leaving group. The cleavage rates of the selected divalent metal independent catalysts are within the same order of magnitude as the rate of metal independent substrate hydrolysis in the hammerhead ribozyme. One of the metal dependent catalysts showed an unexpected preference for Ca2+ instead of Mg2+. In this deoxyribozyme binding of Ca2+ occurred co-operatively whereas binding of Mg2+ did not. Comparison of the secondary structure and reactivity of this catalyst with Mg2+ and Ca2+ suggests that here a special binding pocket for Ca2+ was selected. This deoxyribozyme achieved a rate acceleration of substrate cleavage in the order of at least 10(4) compared to the uncatalysed reaction performing a cleavage mechanism similar to that of the hammerhead or hairpin ribozyme.

Allosteric Regulation↗

PubMed2006

Self-assembly processes in the prebiotic environment.

An important question guiding research on the origin of life concerns the environmental conditions where molecular systems with the properties of life first appeared on the early Earth. An appropriate site would require liquid water, a source of organic compounds, a source of energy to drive polymerization reactions and a process by which the compounds were sufficiently concentrated to undergo physical and chemical interactions. One such site is a geothermal setting, in which organic compounds interact with mineral surfaces to promote self-assembly and polymerization reactions. Here, we report an initial study of two geothermal sites where mixtures of representative organic solutes (amino acids, nucleobases, a fatty acid and glycerol) and phosphate were mixed with high-temperature water in clay-lined pools. Most of the added organics and phosphate were removed from solution with half-times measured in minutes to a few hours. Analysis of the clay, primarily smectite and kaolin, showed that the organics were adsorbed to the mineral surfaces at the acidic pH of the pools, but could subsequently be released in basic solutions. These results help to constrain the range of possible environments for the origin of life. A site conducive to self-assembly of organic solutes would be an aqueous environment relatively low in ionic solutes, at an intermediate temperature range and neutral pH ranges, in which cyclic concentration of the solutes can occur by transient dry intervals.

Earth, Planet↗

PubMed1984

Nucleotide sequence of cucumber-mosaic-virus RNA 2 reveals a translation product significantly homologous to corresponding proteins of other viruses.

The nucleotide sequence of the 3035 residues of RNA 2 (Mr 1.03 X 10(6) ) of the Q strain of cucumber mosaic virus (CMV) was determined by sequencing M13 clones of the RNA 2 cDNA and by dideoxy sequencing using primers prepared either from M13 clones or by chemical synthesis. A single long open reading frame starts at the second AUG from the 5' end of RNA 2 and encodes 839 amino acids (Mr 94333). This frame has flanking regions of 92 nucleotides at the 5' terminus and 423 nucleotides at the 3' terminus. Computer analysis of the nucleotide sequence showed that CMV RNA 2 has a significant homology with RNA 2 of brome mosaic virus (BMV) and alfalfa mosaic virus (AMV) and also with a region for tobacco mosaic virus (TMV) RNA encoding the read-through part of the 183-kDa protein. About 400 amino acids in the central region of the CMV RNA 2 translation product have a striking homology with the corresponding proteins encoded by BMV and AMV and with the read-through part of the TMV 183-kDa protein. Hydrophobicity plots of CMV and BMV RNA translation products also had apparent similarities. It is concluded that CMV is related to BMV, AMV and TMV in order of increasing evolutionary divergence.

Amino Acid Sequence↗

PubMed1993

Formation of reduced carbonaceous matter in basalts and xenoliths: reaction of C-O-H gases on olivine crack surfaces.

It has been suggested that the formation of reduced carbonaceous matter in basalts and mantle xenoliths occurs by heterogeneous reaction of volcanic gas on fresh, chemically active crack surfaces produced by thermal stresses during eruption and cooling. This hypothesis is supported by experiments at 400-800 degrees C on ¿010¿ surfaces of San Carlos olivine exposed to C-O-H gases generated by the decomposition of oxalic acid and oxalic acid dihydrate. Carbonaceous films form readily on these surfaces and achieve thicknesses comparable to those observed in natural samples (a few nanometers) in a matter of minutes. At relatively oxidizing conditions, the carbonaceous films consist principally of C-C and C-H bonded species with lesser amounts of C-O bonded species. At relatively reducing conditions, the carbonaceous films consist of subequal amounts of C-C/C-H, C-O, and metal-C species. Aliphatic and aromatic hydrocarbons and other thermally labile organic species are associated with carbonaceous films in some natural samples but none were detected in experimental samples from this study, leaving open the question of abiotic synthesis of organic matter on crack surfaces in basalts. Regardless, it is clear from the preliminary experiments reported here that crack surfaces in olivine (and probably other silicate minerals and glasses) are capable of stabilizing compounds that otherwise would not be stable in cooling lava.

Carbon↗

PubMed1984

Hot atoms in cosmic chemistry.

High energy chemical reactions and atom molecule interactions might be important for cosmic chemistry with respect to the accelerated species in solar wind, cosmic rays, colliding gas and dust clouds and secondary knock-on particles in solids. "Hot" atoms with energies ranging from a few eV to some MeV can be generated via nuclear reactions and consequent recoil processes. The chemical fate of the radioactive atoms can be followed by radiochemical methods (radio GC or HPLC). Hot atom chemistry may serve for laboratory simulation of the reactions of energetic species with gaseous or solid interstellar matter. Due to the effective measurement of 10(8)-10(10) atoms only it covers a low to medium dose regime and may add to the studies of ion implantation which due to the optical methods applied are necessarily in the high dose regime. Experimental results are given for the systems: C/H2O (gas), C/H2O (solid, 77 K), N/CH4 (solid, 77K) and C/NH3 (solid, 77 K). Nuclear reactions used for the generation of 2 to 3 MeV atoms are: N(p,alpha) 11C, 16O(p,alpha pn) 11C and 12C(d,n) 13N with 8 to 45 MeV protons or deuterons from a cyclotron. Typical reactions products are: CO, CO2, CH4, CH2O, CH3OH, HCOOH, NH3, CH3NH2, cyanamide, formamidine, guanidine etc. Products of hot reactions in solids are more complex than in corresponding gaseous systems, which underlines the importance of solid state reactions for the build-up of precursors for biomolecules in space. As one of the major mechanisms for product formation, the simultaneous or fast consecutive reactions of a hot carbon with two target molecules (reaction complex) is discussed.

Ammonia↗