PubMed Health⌕ Search

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 289 records · Page 16Linked to original sources
PubMed2006

TOF-SIMS evidence of intercalated molecular gases and diffusion-limited reaction kinetics in an alpha particle-irradiated PTFE matrix.

The chemical evolution of poly(tetrafluoroethylene) (PTFE) that is brought about by increasing levels of irradiation with alpha particles is accompanied by the emergence and proliferation of functionalized moieties. Families of reaction products specifically identified in the alpha-irradiated polymer matrix include hydride-, hydroxide-, and oxide-functionalized fluorocarbons. The data also indicate the emergence of hydrogen peroxide (H2O2) and hydrazine (N2H4), but no distinct evidence suggesting the formation of perfluorinated amines, amides, or cyanogens is found. In this article we substantiate the speciation of emergent species and reveal evidence of intercalated molecular gases with which alpha particle-generated radicals may react to form the observed products. Furthermore, we present evidence to suggest that the kinetics of alpha particle-induced reaction is limited by the diffusion of radicals within the polymer matrix. That is to say, chemical additives in the polymer matrix are shown to be scavengers of H*, O*, and F* radicals and limit the rates of reaction that produce functionalized fluorocarbon moieties. Above a threshold dose of alpha particles, the concentration of radicals exceeds that of the scavenger species, and free radical diffusion commences as evidenced by a sudden increase in the yield of reaction products. Samples of PTFE were irradiated to alpha doses in the range of 10(7) to 5 x 10(10) rad with 5.5 MeV 4He2+ ions from a tandem accelerator. Residual gas analysis (RGA) was utilized to monitor the liberation of molecular gases from PTFE during alpha particle irradiation of samples in vacuum. Static time-of-flight SIMS (TOF-SIMS), equipped with a 20 keV C60+ source, was employed to probe chemical changes as a function of alpha particle irradiation. Chemical images and high-resolution mass spectra were collected in both the positive and negative polarities.

Journal Article↗
PubMed2002

Sea transport of animal and vegetable oils and its environmental consequences.

The increasing production-and therefore sea traffic--of vegetable oils has regularly led to spillages during the past 40 years. The accident of Allegra, on October,lst, 1997, in the English Channel gave rise to a spillage of 900 tonnes of palm nut oil. The drift of this solid vegetable oil was followed by aerial observations. Samples of oil were collected in order to analyse its chemical evolution. This study, associated with several bibliographic cases of pollution by non-petroleum oils, shows that drifting oils can mix with floating material to sink or form a crust. They can also be oxidized or disperse and/or be degraded by bacteria. They may also polymerise. The coating properties of vegetable oils act as crude oils to affect sea life, tourism and yachting. As a result, it is necessary to quickly collect the oil after a spillage, using usual equipment (booms and pumps).

Accidents↗
PubMedDate not supplied

Abiotic synthesis of organic compounds under the conditions of submarine hydrothermal systems: a perspective.

Deep-sea hydrothermal systems have been proposed to be likely environments for chemical evolution and the origin of life on Earth. Recently, experiments have, therefore, been carried out in order to test the hypothesis that amino acids can be synthesized under conditions representing hydrothermally altered oceanic crust. The variety of amino acids that have been detected in such experiments corresponds roughly to that reported previously for electric sparking in reducing gas mixtures. The relative yields of the protein amino acids detected are significantly higher than in electric spark discharge experiments, and the overall yields are about an order of magnitude higher. The amino acids are all racemic.

Amino Acids↗
PubMed2002

Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling.

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

Arsenic↗
PubMed1982

Novel formation of alpha-amino acids and their derivatives from oxo acids and ammonia in an aqueous medium.

In the course of a study of chemical evolution of the primeval sea, a novel reaction of carbonyl compounds with ammonia was found. Glyoxylic acid reacted with ammonia to afford N-oxalylglycine, which gave glycine in a 3-20% yield after 6 N HCl hydrolysis. Similarly, glyoxylic acid was treated with methylamine to give N-oxalylsarcosine, which afforded sarcosine in a 9-12% yield upon hydrolysis. Pyruvic acid reacted with ammonia to give N-acetylalanine, which gave alanine in a 1-4% yield upon hydrolysis. These reactions provide a novel and facile route to alpha-amino acids and their derivatives. A mechanism for the reactions is proposed.

Amino Acids↗
PubMed2006

Comparison of the solution behaviour of a pyrite-calcite mixture in batch and unsaturated sand column.

A successful application of reaction transport algorithms to calculate the chemical evolution of natural systems requires accurate methods to compute the rates of mineral/fluid surface reactions. Regarding the transport of radio-nuclides in mining dumps the dissolution of minerals is of special importance. Using a kinetic rate law of the mineral dissolution verified for unsaturated conditions will allow a realistic modelling of the mineral weathering in the environment. Dissolution rates of minerals in an aqueous solution are determined by several characteristics. These are surface reaction rates, morphology of the mineral's surface and, in case it is the unsaturated zone, the degree of the water saturation. For this process, the quantity of the particle surfaces which are in contact with percolating water is most decisive. In order to study the differences of mineral dissolution under saturated and unsaturated conditions batch and column experiments were carried out with a pyrite-calcite mixture. The experimental results were verified by calculations. Comparing the dissolution in batch with those in the column experiment, which was performed with a water flow velocity of 0.64 cm/day and was analyzed in the region of a water saturation of 0.11, one can conclude that only a small portion of about 5% of the grain surface is chemically reactive in this unsaturated flow.

Calcium Carbonate↗
PubMed1999

Pyrite suspended in artificial sea water catalyzes hydrolysis of adsorbed ATP: enhancing effect of acetate.

Minerals have been implicated in different catalytic processes during chemical evolution. It has been proposed that exergonic synthesis of pyrite (FeS2) could have served to promote the endergonic synthesis of biomonomers in early stages of life formation on Earth. The present study was aimed to investigate whether pyrite can adsorb nucleotides and oxo acids in the potentially mild prebiotic conditions found away from the hot hydrothermal vents. It is shown that pyrite strongly adsorbs adenosine 5'-triphosphate in an artificial medium that simulates primordial aqueous environments, and that adsorption is enhanced in the presence of acetate and in an oxygen-free atmosphere. Moreover, the mineral catalyzes the sequential hydrolysis of the gamma and beta phosphoanhydride bonds of the nucleotide.

Acetates↗
PubMed1980

A conformational rationale for the origin of the mechanism of nucleicacid-directed protein synthesis of 'living' organisms.

The physical basis for the natural evolution of a primitive decoding system is presented using the concepts of molecular interactions. Oligoribonucleotides of five residues having U at the 5'-end, a purine at the 3'-end and any combination of three bases in the middle is taken as a primitive tRNA (PIT). From conformational considerations PIT is expected to have U-turn conformation wherein, N3-H3 of base U hydrogen-bonds with phosphate, three residues ahead leaving triplet bases called primitive anticodons (PAC) into a helical conformation, and this creates a cleft between U and PAC. An amino acid can be comfortably nestled into the cleft with the amide hydrogens and carboxyl oxygen hydrogen-bonded to the last purine and the first uridine, while the side-chain can interact with the cleft side of PAC. The other side of PAC is free to base-pair with triplet codons on a longer RNA. Also two PACs can 'recognize' consecutive triplet codons, and this leads to a dynamic interaction in which the amino and carboxyl ends are brought into proximity, making the formation of peptide bond feasible. The cleft formed by different anticodon triplets, broadly speaking, shows preferences for the corresponding amino acids of the presently known codon assignment. Thus the nucleicacid-directed protein synthesis, which is a unique feature of all 'living' organisms is shown to be a natural consequence of a particular way of favourable interaction between nucleic acids and amino acids, and our model provides the missing link between the chemical evolution of small organic molecules and biological evolution through the process of mutations in nucleicacids and nucleicacid-directed protein synthesis.

Animals↗
PubMed2001

Calculation of radiation-induced DNA damage from photons and tritium beta-particles. Part II: Tritium RBE and damage complexity.

Yields of DNA single- and double-strand breaks (SSB and DSB) in nucleosomal DNA were calculated for 137Cs, 70 keV photons and tritium beta-particles by Monte Carlo means. Monte Carlo-generated electron tracks for liquid water were used to model energy deposition. Chemical evolution of a track and interactions between species and DNA following water radiolysis were modelled in an encounter-controlled manner. The calculated relative biological effectiveness (RBE) for DSB production for tritium against 137Cs was 1.2 for the total DSB yield. Tritium beta-particles were slightly more efficient compared to 137Cs in producing complex DSB, defined as DSB accompanied by additional strand breaks. The RBE for complex DSB formation was 1.3. Most complex DSB exhibited associated base damage; the extent of the base damage was similar for all the radiation types considered. Correlated DSB conforming to nucleosome periodicity were observed. However, their frequency was low, of the order of 2% of total DSB. For all the DNA damage endpoints considered and their response to variation of the scavenging environment or DNA conformation no difference was observed between 70 keV photons and tritium beta-particles.

Beta Particles↗
PubMed2005

Modelling the ambient distribution of organic compounds during the august 2003 ozone episode in the southern UK.

A photochemical trajectory model containing speciated emissions of 124 non-methane volatile organic compounds (VOC), and a comprehensive description of the chemistry of VOC degradation, has been used to simulate the chemical evolution of boundary layer air masses arriving at a field campaign site in the southern UK during a widespread and prolonged photochemical pollution event in August 2003. The simulated concentrations and distributions of organic compounds at the arrival location are compared with observations of a series of hydrocarbons and carbonyl compounds, which were measured using GC-FID and multidimensional GC methods. The comparison of the simulated and observed distributions of 34 emitted hydrocarbons provides some support for the magnitude and applied emissions speciation of anthropogenic hydrocarbons, but is indicative of an under representation of the input of biogenic hydrocarbons, particularly at elevated temperatures. Simulations of the detailed distribution of ca. 1250 carbonyl compounds, formed primarily from the degradation of the 124 emitted VOC, focus on 61 aldehydes, ketones, dicarbonyls, hydroxycarbonyls and aromatic aldehydes which collectively account for ca. 90% of the simulated total molar concentration of carbonyls. The simulated distributions indicate that the photolysis of formaldehyde and alpha-dicarbonyls make major contributions to free radical production for the arrival conditions of five case study trajectories. The simulated concentrations of hydroxycarbonyls demonstrate preferential formation of the 1,4-substituted isomers (compared with 1,2- and 1,3-isomers of the same carbon number), which are formed during the initial oxidation sequence of longer chain alkanes.

Air Pollutants↗
PubMed1999

Long-term fate of organics in waste deposits and its effect on metal release.

The long-term chemical evolution in waste deposits and the release of toxic metals was investigated. The degradation of organic matter and hence the potential efflux of heavy metals in a long-term perspective was studied by defining some scenarios for waste deposits containing organic compounds, different longevity and functions of covers and different water and air intrusion rates. The scenarios were based on various transport processes as well as different landfill constructions. The rates of influx of oxygen into both saturated and partially saturated landfills have been estimated. Each scenario takes the form of a mathematical model. The starting point for all the studied cases is the humic phase, i.e. the phase after the methane production has stopped. Based on the different cases studied, it appeared that landfills where the waste is below the water table could have advantages over the other cases. Recognizing that this option is not accepted in most countries we, nevertheless, suggested it should be reevaluated. The main conclusion is that the degradation of humic matter and hence the release of toxic metals can be substantially decreased if potential build-up of hydraulic gradients are avoided and if the landfill is located below the water surface. A conceivable alternative construction would be to place it in a depression--either natural or artificial--and to construct it so that under normal conditions it would always be water-saturated.

Biodegradation, Environmental↗
PubMed1992

Polycyclic aromatic hydrocarbons: primitive pigment systems in the prebiotic environment.

Polycyclic aromatic hydrocarbons (PAH) in the form of polymerized derivatives represent over 90% of the organic material of carbonaceous chondrites. It now appears likely that there was substantial survival of the organic content of meteoritic and cometary infall during late accretion, so that PAH would presumably be major components of the organic inventory present on the prebiotic Earth. An important question relative to chemical evolution and energy transduction is the nature of pigments which could be available to make light energy available to the earliest cellular forms of life. PAH and their derivatives all absorb light in the near UV and blue wavelengths, and are candidates for primitive pigments. We have explored this possibility in a model system consisting of mixtures of pyrene, fluoranthene and pyrene derivatives with hexadecane, dispersed in dilute salt solutions. Upon illumination, photochemical oxidation of the hexadecane occurs, with long-chain amphiphiles such as 2-hexadecanone and 2-hexadecanol as products. Because the reaction proceeds under strictly anaerobic conditions, the source of oxygen is apparently water. We also observed acid pH shifts during illumination. Photochemical production of hydrogen ion is significant, in that chemiosmotic proton gradients across membranes are used by all contemporary cells as a source of energy for ATP synthesis and nutrient transport. To test whether the protons could be used to transduce light energy into a useful form, PAH derivatives were included in lipid bilayer membranes (liposomes). Upon illumination, protons (or acidic products) were produced and accumulated inside the vesicles, so that substantial pH gradients were established across the membranes, acid inside. We conclude that PAH dissolved in aliphatic hydrocarbons absorb light energy and use it to oxidize the hydrocarbon to long-chain amphiphilic molecules. The oxidation is accompanied by release of protons. If PAH derivatives are included in the bilayer membrane of lipid vesicles, protons accumulate within the membrane-bounded volumes to form proton gradients. This system provides a useful model of a primitive photochemical reaction in which light energy is transduced into potentially useable forms.

Alkanes↗
PubMed2001

Monte Carlo calculation of the primary radical and molecular yields of liquid water radiolysis in the linear energy transfer range 0.3-6.5 keV/micrometer: application to 137Cs gamma rays.

Monte Carlo simulations of the radiolysis of neutral liquid water and 0.4 M H(2)SO(4) aqueous solutions at ambient temperature are used to calculate the variations of the primary radical and molecular yields (at 10(-6)s) as a function of linear energy transfer (LET) in the range approximately 0.3 to 6.5 keV/micrometer. The early energy deposition is approximated by considering short (approximately 20-100 micrometer) high-energy (approximately 300-6.6 MeV) proton track segments, over which the LET remains essentially constant. The subsequent nonhomogeneous chemical evolution of the reactive species formed in these tracks is simulated by using the independent reaction times approximation, which has previously been used successfully to model the radiolysis of water under various conditions. The results obtained are in good general agreement with available experimental data over the whole LET range studied. After normalization of our computed yields relative to the standard radical and molecular yields for (60)Co gamma radiation (average LET approximately 0.3 keV/micrometer), we obtain empirical relationships of the primary radiolytic yields as a function of LET over the LET range studied. Such relationships are of practical interest since they allow us to predict a priori values of the radical and molecular yields for any radiation from the knowledge of the average LET of this radiation only. As an application, we determine the corresponding yields for the case of (137)Cs gamma radiation. For this purpose, we use the value of approximately 0.91 keV/micrometer for the average LET of (137)Cs gamma rays, chosen so that our calculated yield G(Fe(3+)) for ferrous-ion oxidation in air-saturated 0.4 M sulfuric acid reproduces the value of 15.3 molecules/100 eV for this radiation recommended by the International Commission on Radiation Units and Measurements. The uncertainty range on those primary radical and molecular yields are also determined knowing the experimental error (approximately 2%) for the measured G(Fe(3+)) value. The following values (expressed in molecules/100 eV) are obtained: (1) for neutral water: G(e(-)(aq)) = 2.50 +/- 0.16, G(H(.)) = 0.621 +/- 0.019, G(H(2)) = 0.474 +/- 0.025, G((.)OH) = 2.67 +/- 0.14, G(H(2)O(2)) = 0.713 +/- 0.031, and G(-H(2)O) = 4.08 +/- 0.22; and (2) for 0.4 M H(2)SO(4) aqueous solutions: G(H(.)) = 3.61 +/- 0.09, G(H(2)) = 0.420 +/- 0.019, G((.)OH) = 2.78 +/- 0.12, G(H(2)O(2)) = 0.839 +/- 0.037, and G(-H(2)O) = 4.46 +/- 0.16. These computed values are found to differ from the standard yields for (60)Co gamma rays by up to approximately 6%.

Cesium Radioisotopes↗
PubMed1999

Nonenzymatic oligomerization reactions on templates containing inosinic acid or diaminopurine nucleotide residues.

The template-directed oligomerization of nucleoside-5'-phosphoro-2-methyl imidazolides on standard oligonucleotide templates has been studied extensively. Here, we describe experiments with templates in which inosinic acid (I) is substituted for guanylic acid, or 2,6-diaminopurine nucleotide (D) for adenylic acid. We find that the substitution of I for G in a template is strongly inhibitory and prevents any incorporation of C into internal positions in the oligomeric products of the reaction. The substitution of D for A, on the contrary, leads to increased incorporation of U into the products. We found no evidence for the template-directed facilitation of oligomerization of A or I through A-I base pairing. The significance of these results for prebiotic chemistry is discussed.

2-Aminopurine↗
PubMed1993

New angiotensin I isolated from a reptile, Alligator mississippiensis.

Angiotensin I (ANG I) of the American alligator Alligator mississippiensis was isolated from incubates of homologous plasma and kidney extract, and its amino acid sequence was determined as H-Asp-Arg-Val-Tyr-Val-His-Pro-Phe-Ala-Leu-OH. The presence of strongly hydrophobic alanine at position 9 is unusual among ANGs I sequenced to date. Since alanine can be converted to serine by a one-point mutation of the triplet nucleotides, the phylogenetic proximity of the alligator to birds, whose ANG I has serine at position 9, is confirmed by the chemical evolution of the hormone structure. The alligator [Asp1,Val5,Ala9] ANG I increased arterial blood pressure of conscious alligators, but it was no more potent than avian [Asp1,Val5,Ser9] ANG I. The alligator ANG I was also equipotent to the homologous ANG I in the quail and rat. It is concluded that substitutions at position 9 have little influence on the vasopressor activity of ANG I.

Alligators and Crocodiles↗
PubMed1976

The genetic code and the origin of life.

The problem of the origin of life understandably counts as one of the most exciting questions in the natural sciences, but in spite of almost endless speculation on this subject, it is still far from its final solution. The complexity of the functional correlation between recent nucleic acids and proteins can e.g. give rise to the assumption that the genetic code (and life) could not originate on the Earth. It was Portelli (1975) who published the hypothesis that the genetic code could not originate during the history of the Earth. In his opinion the recent genetic code represents the informational message transmitted by living systems of the previous cycle of the Universe. Here however, we defend the existence of a certain strategy in the syntheses of the genetic code during the history of the Earth. The strategy of correlation between amino acid and nucleotide polymers made an increasing velocity of the chemical evolution possible, that is, it increased the velocity of formation of the genetic code. Thus, life with the recent genetic code could originate on the Earth within the present cycle of the Universe.

Amino Acids↗
PubMed1996

The delivery of organic matter from asteroids and comets to the early surface of Mars.

Carbon delivered to the Earth by interplanetary dust particles may have been an important source of pre-biotic organic matter (Anders, 1989). Interplanetary dust is shown to deliver an order-of-magnitude higher surface concentration of carbon onto Mars than onto Earth, suggesting interplanetary dust may be an important source of carbon on Mars as well.

Carbon↗