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On the stereoselective aminoacylation of RNA.

Aminoacylation of the "internal" 2'hydroxyl groups of poly(A) with the imidazolide of racemic DL-leucine resulted in the formation of an enantiomeric excess of the D-ester, whereas aminoacylation with the imidazolide of racemic N-3,5-dinitrobenzoyl-DL-leucine gave an enantiomeric excess of the L-ester. Comparison of these results with those obtained earlier for alanine shows that the larger side chain tends to favor the formation of the D-ester. High resolution proton magnetic resonance spectroscopy was performed on the D- and L-alanyl "internal" 2'-esters of 3'5'-ApA. The resonance of the side chain methyl group of the D-ester is upfield from that of the L-ester, and the separation of the peaks increases with a decrease in temperature.

Acylation↗

The origin of adaptation and dyssymmetry in the evolution of autocatalytic systems.

The evolution of open systems that include several autocatalytic processes in parallel or in series is mathematically analyzed. For the case of two reactions in parallel, such systems progressively and finally select the reaction pathway which involves the better autocatalyst. The effect of parameters influencing the rate of this evolution is discussed. Where catalysts are strictly equivalent, e.g. enantiomers in a symmetrical surrounding, the evolution is amplified by fluctuations and retains finally only one reaction pathway, if the autocatalytic rates of reactions are more than proportional to the catalyst concentrations. When including two reactions in series, these open systems are also able to give oscillations.

Catalysis↗

Hydrogen cyanide polymers on comets.

The original presence on cometary nuclei of frozen volatiles such as methane, ammonia and water makes them ideal sites for the formation and condensed-phase polymerization of hydrogen cyanide. We propose that the non-volatile black crust of comet Halley consists largely of such polymers. Dust emanating from Halley's nucleus, contributing to the coma and tail, would also arise partly from these solids. Indeed, secondary species such as CN have been widely detected, as well as HCN itself and particles consisting only of H, C and N. Our continuing investigations suggest that the yellow-orange-brown-black polymers are of two types: ladder structures with conjugated -C=N- bonds, and polyamidines readily converted by water to polypeptides. These easily formed macromolecules could be major components of the dark matter observed on the giant planets Jupiter and Saturn, as well as on outer solar system bodies such as asteroids, moons and other comets. Implications for prebiotic chemistry are profound. Primitive Earth may have been covered by HCN polymers either through cometary bombardment or by terrestrial happenings of the kind that brought about the black crust of Halley. The resulting proteinaceous matrix could have promoted the molecular interactions leading to the emergence of life.

Evolution, Chemical↗

The initiation of biological processes on Earth: summary of empirical evidence.

With the currently available geological record at band, the existence of life on this planet as from at least 3.8 Gyr ago seems so firmly established as to be virtually unassailable. Specifically, various disparate lines of evidence have merged to indicate (1) that the surface of the Archaean Earth had hosted prolific microbial ecosystems as is testified by a quasi-continuous record of microbialites ("stromatolites") and associated microfossils of prokaryotic affinity over 3.5, if not 3.8 Gyr of geological history, and (2) that the sedimentary carbon record has preserved the isotopic signature of autotrophic (notably photosynthetic) carbon fixation over the same time span. With the observed enrichment of isotopically light carbon in sedimentary organic matter largely consonant with the bias in favor of 12C during photosynthesis, the mainstream of the carbon isotope record can be best explained as geochemical manifestation of the isotope discriminating properties of the ribulose-1,5-bisphosphate (RuBP) carboxylase reaction of the Calvin cycle suggesting an extreme degree of evolutionary conservatism in the biochemistry of autotrophic carbon fixation. As a consequence, partial biological control of the geochemical carbon cycle was established already during Early Archaean times and fully operative by the time of formation of the Earth's earliest sediments.

Carbon↗

Quantitative analysis of mutation and selection in self-replicating RNA.

Mutation and selection as principles of Darwinian evolution have contributed a wealth to qualitative insight and understanding of complex biological organizations. However, for quantitative measurements of Darwinian evolution, only model systems are sufficiently simple to allow calculation of values for the relevant evolution parameters. The model system used for our study comprises short-chained RNA species whose self-replication is catalyzed by Q beta replicase. In this system, phenotypic expression of a genotype is reduced to its efficiency in directing its own synthesis. The mechanism of single-stranded RNA reproduction is well understood: RNA synthesis profiles can be described by compact equations. The selection behaviour of competing RNA species can be precisely predicted, using these equations, from kinetic parameters of the species: at low concentrations, RNA species are selected for overall growth rate (fecundity), at higher concentrations, for rapid binding of replicase (selection for competition), and at still higher concentrations, for minimizing losses caused by formation of inactive double strands. Finally, an ecosystem may be established where the different species coexist, their relative concentrations being functions of their kinetic parameters. The analysis of competition and selection can be extended to mutants of a species. Experimental conditions can be found where quantitative measurement of mutation rates and selective values of mutants is possible. The interplay of mutation and selection results in establishing a quasispecies distribution where mutants are represented according to their rates of mutational formation and their selective values. Replicating RNA clones, when amplified, rapidly build up quasispecies distributions containing pronounced "hot spots", produced predominantly by error propagation of nearly neutral mutants. The primitive model system shows the same complex Darwinian behaviour as observed in evolution of biological systems. In the absence of extraneously added template, Q beta replicase synthesizes after long lag times self-replicating RNA de novo. In a first step, nucleoside triphosphates are condensed randomly; self-replicating templates produced by chance are amplified and optimized.

Allolevivirus↗

From organic chemistry in small bodies of the solar system to low temperature chemistry in the universe. Preface.

A COSPAR two days Symposium has been dedicated to "Prebiotic chemistry in Space" at the COSPAR Plenary Meeting, (Hamburg, Germany, July 1994). This Symposium was jointly organized by Commissions B (Space studies of the Earth-Moon system, planets and small bodies of the solar system) and F (Life sciences as related to space). Its goal was to review, from an interdisciplinary approach, our knowledge on organic and prebiotic chemistry in small bodies of the Solar System, and on low temperature chemistry and exobiology. The Symposium was sponsored by COSPAR and the IAU (session 1), ESA, NASA, and ISSOL (session 2).

Cosmic Dust↗

The formation of organic molecules in astronomical ices.

An absorption feature at 3.4 micrometers has been observed in various lines-of-sight through the diffuse interstellar medium. Its position and width lead to an identification with the C-H stretching mode of solid organic material. A possible mechanism for the production of organic solids in the interstellar medium is UV photoprocessing of icy mantles which accrete on dust grains in dense clouds. Furthermore, thermally induced reactions involving formaldehyde molecules in the mantles could be an important source of organics. Laboratory simulation of these processes shows that a large variety of oxygen- and nitrogen-rich species may be produced. It is shown that the occurrence of periodic transient heating events plays an important role in the production of organic material in the ice mantles. Finally, it is pointed out how future missions like the Infrared Space Observatory (ISO) as well as analysis of comet material by Rosetta may be able to clarify the nature and evolution of interstellar organics.

Carbon Monoxide↗

Electrical excitability of proteinoid microspheres composed of basic and acidic proteinoids.

Material flow equilibration, an endogenous interaction adjustment process underlying fulfillment of material flow continuity during material self-assembly, also underlies electrical excitability observed in the proteinoid microspheres as simulated models of the protocell. The spikings of the membrane potentials are attributed to a singular character of the interaction rate coefficients measuring the strengths of the coupling between basic and acidic proteinoids, in which the rates change singularly with time due to material flow equilibration.

Biological Evolution↗

Physicochemical properties of signal receptor domains as the basis for sequence comparison.

1. An algorithm of sequence comparison based on average bulkiness of amino acids in protein domains and not requiring sequence alignment is described. 2. A complete evolutionary tree of the signal receptor proteins is built. The STE2 proteins are shown to belong to this family. 3. Factorial analysis of average bulkiness makes it possible to discriminate functional and intraspecies differences between proteins.

Algorithms↗

On the origin of biological systems and the role of poly-nucleotides -- the initiation of evolution, the structural basis of the genetic code and the mechanism of protein biosynthesis.

There is much information on the nature and function of biological systems in the structures of the small molecules that affect them and in the biosynthetic and other reactions in which they are involved. Combining this with biochemical and polynucleotide sequence information allows us to derive explanations for a number of biological problems that earlier were unclear or even quite obscure. Thus polynucleotide systems give a good account of the origin of life, of the genetic code and of the function of the ribosomal mechanism of protein biosynthesis. It is apparent that polynucleotides play a more important role than has been fully appreciated.

Biological Evolution↗

Impact-shocked rocks--insights into Archean and extraterrestrial microbial habitats (and sites for prebiotic chemistry?).

Impact-shocked gneiss shocked to greater than 10 GPa in the Haughton impact structure in the Canadian High Arctic has an approximately 25-times greater pore surface area than unshocked rocks. These pore spaces provide microhabitats for a diversity of heterotrophic microorganisms and in the near-surface environment of the rocks, where light levels are sufficient, cyanobacteria. Shocked rocks provide a moisture retaining, UV protected microenvironment. During the Archean, when impact fluxes were more than two orders of magnitude higher than today, the shocked-rock habitat was one of the most common terrestrial habitats and might have provided a UV-shielded refugium for primitive life. These potential habitats are in high abundance on Mars where impact crater habitats could have existed over geologic time periods of billions of years, suggesting that impact-shocked rocks are important sites to search for biomolecules in extraterrestrial life detection strategies. In addition to being favourable sites for life, during the prebiotic period of planetary history impact-shocked rocks might have acted as a site for the concentration of reactants for prebiotic syntheses.

Arctic Regions↗

Self-organizing proto-replicators and the origin of life.

Standard theories suggest that the first informational replicator involved RNA molecules (or a more primitive analogue) and that a preliminary step for the development of such replicating systems may have been the emergence of subunits capable of forming chains and interchain pairings. Following these hypotheses, this discussion describes various abstract simulations designed to investigate the structures resulting from such interactions for generalised subunits. Three classes of pairing strategy were considered for a range of subunit concentrations. The resulting dynamic self-organization of the systems produced high levels of structural complexity (some at low subunit concentrations and in the presence of disruptive subunits) and a significantly increased percentage of complementary base pairing (particularly in the more substantial structures). These properties of the systems, which did not require pre-existing replicators, templates or functional catalysts, were shown to be sensitive to the form of pairing strategy, subunit concentrations and various conditions that could theoretically be altered by products of the systems. Though no systems behaved as a replicator, some possessed collections of properties from which a replicating system might theoretically be constructed without requiring the introduction of additional classes of properties. The implications of such systems were considered with respect to the origin of life.

Catalysis↗

Catalytic activity of hammerhead ribozymes in a clay mineral environment: implications for the RNA world.

The hypothesized RNA-based world would have required the presence of a protected environment in which RNA, or an RNA-like molecule, could originate and express its biological activity. Recent studies have indicated that RNA molecules adsorbed/bound on clay minerals are able to persist in the presence of degrading agents, to interact with surrounding molecules, and to transmit the information contained in their nucleotide sequences. In this study, we assessed the ability of RNA molecules with catalytic activity to perform a specific reaction in a mineral environment. For this purpose, we investigated the self-cleavage reaction of the hammerhead ribozyme of the Avocado Sun Blotch Viroid (ASBVd), both in the monomeric and in dimeric forms. The monomeric transcript was tightly bound on the clay mineral montmorillonite to form a stable complex, while the behaviour of the dimeric transcript was studied in the presence of the clay particles in the reaction mixture. The results indicated that the hammerhead ribozyme was still active when the monomeric transcript was adsorbed on the clay surface, even though its efficiency was reduced to about 20% of that in solution. Moreover, the self-cleavage of clay-adsorbed molecule was significantly enhanced ( approximately four times) by the presence of the 5' reaction product. The self-cleavage reaction of the dimeric transcript in the presence of montmorillonite indicated that the mineral particles protected the RNA molecules against aspecific degradation and increased the rate of cleavage kinetics by about one order of magnitude. These findings corroborate the hypothesis that clay-rich environments would have been a good habitat in which RNA or RNA-like molecules could originate, accumulate and undergo Darwinian evolutionary processes, leading to the first living cells on Earth.

Adsorption↗

C1q and tumor necrosis factor superfamily: modularity and versatility.

C1q is the target recognition protein of the classical complement pathway and a major connecting link between innate and acquired immunity. As a charge pattern recognition molecule of innate immunity, C1q can engage a broad range of ligands via its globular (gC1q) domain and modulate immune cells, probably via its collagen region. The gC1q signature domain, also found in many non-complement proteins, has a compact jelly-roll beta-sandwich fold similar to that of the multifunctional tumor necrosis factor (TNF) ligand family. The members of this newly designated 'C1q and TNF superfamily' are involved in processes as diverse as host defense, inflammation, apoptosis, autoimmunity, cell differentiation, organogenesis, hibernation and insulin-resistant obesity. This review is an attempt to draw structural and functional parallels between the members of the C1q and TNF superfamily.

Amino Acid Sequence↗