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At least 109 records · Page 6

Protein sequences and redox titrations indicate that the electron acceptors in reaction centers from heliobacteria are similar to Photosystem I

Photosynthetic reaction centers isolated from Heliobacillus mobilis exhibit a single major protein on SDS-PAGE of 47 000 Mr. Attempts to sequence the reaction center polypeptide indicated that the N-terminus is blocked. After enzymatic and chemical cleavage, four peptide fragments were sequenced from the Heliobacillus mobilis apoprotein. Only one of these sequences showed significant specific similarity to any of the protein and deduced protein sequences in the GenBank data base. This fragment is identical with 56% of the residues, including both cysteines, found in highly conserved region that is proposed to bind iron-sulfur center Fx in the Photosystem I reaction center peptide that is the psaB gene product. The similarity to the psaA gene product in this region is 48%. Redox titrations of laser-flash-induced photobleaching with millisecond decay kinetics on isolated reaction centers from Heliobacterium gestii indicate a midpoint potential of -414 mV with n = 2 titration behavior. In membranes, the behavior is intermediate between n = 1 and n = 2, and the apparent midpoint potential is -444 mV. This is compared to the behavior in Photosystem I, where the intermediate electron acceptor A1, thought to be a phylloquinone molecule, has been proposed to undergo a double reduction at low redox potentials in the presence of viologen redox mediators. These results strongly suggest that the acceptor side electron transfer system in reaction centers from heliobacteria is indeed analogous to that found in Photosystem I. The sequence similarities indicate that the divergence of the heliobacteria from the Photosystem I line occurred before the gene duplication and subsequent divergence that lead to the heterodimeric protein core of the Photosystem I reaction center.

NASA Discipline Number 52-30↗

Experimental studies in vortex pair motion coincident with a liquid reaction

An experimental examination of the coincidence of a liquid reaction (acid/base) with the formation of a vortex pair structure is described in which emphasis is placed on the evolution of the strained diffusion layer and reacted core structures. Flow visualization of the reaction process is achieved via the technique of chemically sensitive LIF. The observed growth of reacted core structures associated with each vortex is compared with theoretically predicted behavior (Marble, 1983; Karagozian and Marble, 1986). Vortex pair separation is also compared with theoretical correlations, and the relevance of the analogy between a fast liquid reaction and a gaseous reaction is discussed.

Karagozian, A. R.↗

ISSOL Meeting, 7th, Barcelona, Spain, July 4-9, 1993

The journal issue consists of abstracts presented at the International Society for the Study of the Origins of Life (ISSOL) conference. Topics include research on biological and chemical evolution including prebiotic evolution: cosmic and terrestrial; mechanisms of abiogenesis including synthesis and reactions of biomonomers; and analysis of cometary matter and its possible relationship to organic compounds on Earth. Theories and research on origins of ribonucleic acids (RNA), deoxyribonucleic acid (DNA), and other amino acids and complex proteins including their autocatalysis, replication, and translation are presented. Abiotic synthesis of biopolymers, mechanisms of the Genetic Code, precellular membrane systems and energetics are considered. Earth planetary evolution including early microfossils and geochemical conditions and simulations to study these conditions are discussed. The role of chirality in precellular evolution and the taxonomy and phylogeny of very simple organisms are reported. Past and future explorations in exobiology and space research directed toward study of the origins of life and solar system evolution are described.

Ferris, James P.↗

The possible role of soluble salts in chemical evolution

A model for a prebiotic environment in which concentration, condensation, and chemical evolution of biomolecules could have occurred is proposed. The principal reactions expected of proteins, nucleic acids, lipids, and some of their precursors in this environment are discussed. The model is based on the concept of a fluctuating system in which hydration and dehydration processes occur in a cyclic manner, with allowance for high concentrations of soluble salts, such as chlorides and sulfates. It is concluded that the proposed prebiotic environment with its dynamical characteristics is a plausible model for the chemical evolution from biomonomers through random oligomers toward self-replicating chemical systems.

Lahav, N.↗

The origin of life

Research in the areas of precambrian paleontology, chemical evolution of genetically important monomers, prebiotic dehydration-condensation reactions, organic compounds in meteorites and interstellar space, and biological exploration of the planets is summarized. Fossils in precambrian cherts and findings of eukaryotic cells are described, and recent investigations of prebiotic conditions, energy sources, and starting materials for genetic molecules are outlined. Studies of homogeneous and heterogeneous dehydrations and of nonaqueous thermal dehydrations are described. The detection of amino acids, purines, and pyrimidines in meteorites and of biologically significant molecules in interstellar clouds is discussed, as well as the possibilities of life on Jupiter, Mars, and Titan.

Horowitz, N. H.↗

Spectroscopic diagnostics of organic chemistry in the protostellar environment

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

Ethers/analysis/chemical synthesis/chemistry↗

Mathematical Modeling of the Origins of Life

The emergence of early metabolism - a network of catalyzed chemical reactions that supported self-maintenance, growth, reproduction and evolution of the ancestors of contemporary cells (protocells) was a critical, but still very poorly understood step on the path from inanimate to animate matter. Here, it is proposed and tested through mathematical modeling of biochemically plausible systems that the emergence of metabolism and its initial evolution towards higher complexity preceded the emergence of a genome. Even though the formation of protocellular metabolism was driven by non-genomic, highly stochastic processes the outcome was largely deterministic, strongly constrained by laws of chemistry. It is shown that such concepts as speciation and fitness to the environment, developed in the context of genomic evolution, also held in the absence of a genome.

Pohorille, Andrew↗

A Biological Perspective on the Meaning of Time

We have become impatient waiting for a web page to load, but the first member of our species evolved about 150,000 years ago - a geological instant as brief and as transitory as a text message. The shortest generation time of a bacterium is a sprint at under ten minutes, whereas a 200-year old whale, turtle or tree is not unknown. Life is a phenomenon that integrates processes ranging from the near instantaneous reactions of photosynthesis to the more stately pace of evolution. Here I will elucidate these processes with radically different time scales that go to creating and maintaining the diversity of life on earth, the clocks that nature uses to time them, and how modern biology is being used to alter the natural time scales.

Time↗

The evolution equation for the flame surface density in turbulent premixed combustion

The mean reaction rate in flamelet models for turbulent premixed combustion depends on two basic quantities: a mean chemical rate, called the flamelet speed, and the flame surface density. Our previous work had been primarily focused on the problem of the structure and topology of turbulent premixed flames, and it was then determined that the flamelet speed, when space-averaged, is only weakly sensitive to the turbulent flow field. Consequently, the flame surface density is the key quantity that conveys most of the effects of the turbulence on the rate of energy release. In flamelet models, this quantity is obtained via a modeled transport equation called the Sigma-equation. Past theoretical work has produced a rigorous approach that leads to an exact but unclosed formulation for the turbulent Sigma-equation. In the exact Sigma-equation, it appears that the dynamical properties of the flame surface density are determined by a single parameter, namely the turbulent flame stretch. Unfortunately, the turbulent flame stretch as well as the flame surface density is not available from experiments, and, in the absence of experimental data, little is known on the validity of the closure assumptions used in current flamelet models. Direct Numerical Simulation (DNS) is the alternative approach to get basic information on these fundamental quantities. In the present work, three-dimensional DNS of premixed flames in isotropic turbulent flow is used to estimate the different terms appearing in the Sigma-equation. A new methodology is proposed to provide the source and sink terms for the flame surface density, resolved both temporally and spatially throughout the turbulent flame brush. Using this methodology, our objective is to extract the turbulent flame stretch from the DNS data base and then perform extensive comparisons with flamelet models. Thanks to the detailed information produced by the DNS-based analysis, it is expected that this type of comparison will not only underscore the shortcomings of current models, but also suggest ways to improve them.

Trouve, Arnaud↗

Flammability: A Review and Analysis

With its founding in 1975, Committee G-4 of the American Society for Testing and Materials (ASTM) embarked on the process of defining the flammability of metallic materials in oxygen-enriched atmospheres. In this process, they are joined by the National Aeronautics and Space Administration (NASA), the National Fire Protection Association (NFPA), and the Compressed Gas Association (CGA). Although none of these organizations has explicitly defined flammability, the following definitions and statements provide a composite understanding of the concept: 1. "This Standard Guide (ASTM G94-92) is concerned primarily with the properties of a material associated with its relative susceptibility to ignition and propagation of combustion." 2. "A material is considered flammable at the maximum use pressure if at least one sample burns more than 6 in. (15.2 cm). At least, five samples must be tested." NASA 3. "Flammable: Capable, when ignited of maintaining combustion under the specified environmental conditions." NFPA 53. 4. "Combustion: A complex sequence of chemical reactions between a fuel and an oxidant accompanied by the evolution of heat, and usually, the emission of light." NFPA 53. and 5. "A safe oxygen-piping transmission or distribution system is one that is designed and installed in accordance with all applicable codes and regulations for the service conditions and locations involved and further meets the special requirements for oxygen services." CGA-G4 Flammability thus equates, after ignition, to propagation of combustion, synonymous with steady state burning, under specified environmental conditions. Properties for which quantitative values are given in ASTM G94-92 and which are used to describe metals flammability consistent with the concept of steady state burning are either system independent properties, such as, enthalpies of reaction, burn ratios, flame temperatures, thermal conductivity, and heat release; or system dependent properties, such as, oxygen index, promoted combustion, threshold pressure and burn rates. Each property is reviewed and analyzed as to whether it provides an absolute or relative measure for flammability. It is shown that burn ratio, as applied to the actual steady state combustion condition, approaches the desired absolute measure of flammability.

Wilson, D. Bruce↗

Analysis of Hydrodynamic (Landau) Instability in Liquid-Propellant Combustion at Normal and Reduced Gravity

The burning of liquid propellants is a fundamental combustion problem that is applicable to various types of propulsion and energetic systems. The deflagration process is often rather complex, with vaporization and pyrolysis occurring at the liquid/gas interface and distributed combustion occurring either in the gas phase or in a spray. Nonetheless, there are realistic limiting cases in which combustion may be approximated by an overall reaction at the liquid/gas interface. In one such limit, the gas flame occurs under near-breakaway conditions, exerting little thermal or hydrodynamic influence on the burning propellant. In another such limit, distributed combustion occurs in an intrusive regime, the reaction zone lying closer to the liquid/gas interface than the length scale of any disturbance of interest. Finally, the liquid propellant may simply undergo exothermic decomposition at the surface without any significant distributed combustion, such as appears to occur in some types of HydroxylAmmonium Nitrate (HAN)-based liquid propellants at low pressures. Such limiting models have recently been formulated,thereby significantly generalizing earlier classical models that were originally introduced to study the hydrodynamic stability of a reactive liquid/gas interface. In all of these investigations, gravity appears explicitly and plays a significant role, along with surface tension, viscosity, and, in the more recent models, certain reaction-rate parameters associated with the pressure and temperature sensitivities of the reaction itself. In particular, these parameters determine the stability of the deflagration with respect to not only classical hydrodynamic disturbances, but also with respect to reactive/diffusive influences as well. Indeed, the inverse Froude number, representing the ratio of buoyant to inertial forces, appears explicitly in all of these models, and consequently, in the dispersion relation that determines the neutral stability boundaries beyond which steady, planar burning is unstable to nonsteady, and/or nonplanar (cellular) modes of burning. These instabilities thus lead to a number of interesting phenomena, such as the sloshing type of waves that have been observed in mixtures of HAN and TriEthanolAmmonium Nitrate (TEAN) with water. Although the Froude number was treated as an O(1) quantity in these studies, the limit of small inverse Froude number corresponding to the microgravity regime is increasingly of interest and can be treated explicitly, leading to various limiting forms of the models, the neutral stability boundaries, and, ultimately, the evolution equations that govern the nonlinear dynamics of the propagating reaction front. In the present work, we formally exploit this limiting parameter regime to compare some of the features of hydrodynamic instability of liquid-propellant combustion at reduced gravity with the same phenomenon at normal gravity.

Margolis, Stephen B.↗

Deuterated PAHs in Space

The cosmic deuterium to hydrogen (D/H) ratio is of key importance from a cosmological and stellar evolution perspective since deuterium originates from big-bang nucleosynthesis and is destroyed by stellar thermonuclear reactions. Further, from the interstellar perspective, the galactic distribution of deuterium and the D/H ratio among various molecular species also traces interstellar chemical evolution. Over the past few decades, radio observations have enabled the study of a handful of small, deuterated interstellar species. However, the number of deuterated species detected and environments probed are limited, raising issues of selection effects that hamper generalization and applications to other environments. Infrared spectroscopy of the interstellar medium offers a distinct advantage in this regard as the extent of deuteration of entire chemical families, rather than one species, can be probed. These observations require spaceborne telescopes because the molecular vibrations involving D which produce the strongest IR bands fall in spectral regions which are obscured by terrestrial CO2 absorption. Here we report the tentative detection of the C-D stretching vibration from deuterated interstellar polycyclic aromatic hydrocarbons in the Orion nebula. Since the PAH emission features are widespread and probe many different types of cosmic environments, follow up observations of deuterated PAHs will provide fundamental, far reaching new insight and perspective into galactic and extragalactic processes.

Peeters, Els↗

A Powerful Toolkit for Synthetic Biology: Over 3.8 Billion Years of Evolution

The combination of evolutionary with engineering principles will enhance synthetic biology. Conversely, synthetic biology has the potential to enrich evolutionary biology by explaining why some adaptive space is empty, on Earth or elsewhere. Synthetic biology, the design and construction of artificial biological systems, substitutes bio-engineering for evolution, which is seen as an obstacle. But because evolution has produced the complexity and diversity of life, it provides a proven toolkit of genetic materials and principles available to synthetic biology. Evolution operates on the population level, with the populations composed of unique individuals that are historical entities. The source of genetic novelty includes mutation, gene regulation, sex, symbiosis, and interspecies gene transfer. At a phenotypic level, variation derives from regulatory control, replication and diversification of components, compartmentalization, sexual selection and speciation, among others. Variation is limited by physical constraints such as diffusion, and chemical constraints such as reaction rates and membrane fluidity. While some of these tools of evolution are currently in use in synthetic biology, all ought to be examined for utility. A hybrid approach of synthetic biology coupled with fine-tuning through evolution is suggested

Rothschild, Lynn J.↗

A transport equation for the scalar dissipation in reacting flows with variable density: First results

Although the different regimes of premixed combustion are not well defined, most of the recent developments in turbulent combustion modeling are led in the so-called flamelet regime. The goal of these models is to give a realistic expression to the mean reaction rate (w). Several methods can be used to estimate (w). Bray and coworkers (Libby & Bray 1980, Bray 1985, Bray & Libby 1986) express the instantaneous reaction rate by means of a flamelet library and a frequency which describes the local interaction between the laminar flamelets and the turbulent flowfield. In another way, the mean reaction rate can be directly connected to the flame surface density (Sigma). This quantity can be given by the transport equation of the coherent flame model initially proposed by Marble & Broadwell 1977 and developed elsewhere. The mean reaction rate, (w), can also be estimated thanks to the evolution of an arbitrary scalar field G(x, t) = G(sub O) which represents the flame sheet. G(x, t) is obtained from the G-equation proposed by Williams 1985, Kerstein et al. 1988 and Peters 1993. Another possibility proposed in a recent study by Mantel & Borghi 1991, where a transport equation for the mean dissipation rate (epsilon(sub c)) of the progress variable c is used to determine (w). In their model, Mantel & Borghi 1991 considered a medium with constant density and constant diffusivity in the determination of the transport equation for (epsilon(sub c)). A comparison of different flamelet models made by Duclos et al. 1993 shows the realistic behavior of this model even in the case of constant density. Our objective in this present report is to present preliminary results on the study of this equation in the case of variable density and variable diffusivity. Assumptions of constant pressure and a Lewis number equal to unity allow us to significantly simplify the equation. A systematic order of magnitude analysis based on adequate scale relations is performed on each term of the equation. As in the case of constant density and constant diffusivity, the effects of stretching of the scalar field by the turbulent strain field, of local curvature, and of chemical reactions are predominant. In this preliminary work, we suggest closure models for certain terms, which will be validated after comparisons with DNS data.

Mantel, T.↗

On the evolution of slowly accreting neutron stars

In the light of recent calculations of pycnonuclear reaction rates for light elements, we consider the problem of slow interstellar accretion onto old, possibly magnetized neutron stars. We argue that accretion will occur at the Hoyle-Lyttleton rate after the star has spun down in less than about 10 exp 9 yr. A deep ocean of liquid hydrogen and helium, extending down to depths about 100 m, will cover the surface of the star once it has accreted about 10 exp 25 g of gas. Beneath the ocean will be a layer of almost pure solid O-16 which undergoes two-stage electron capture to C-16 above a pressure 2.7 x 10 exp 28 dyne/sq cm, corresponding to an accreted mass of about 10 exp 27 g. Taking into account the presence of multiple layers of distinct chemical composition, we conclude that the crust will be stable to small perturbations under the conditions envisaged for instellar accretion. A thick layer of up to 10 exp 27 g of metastable C-16 will then accumulate. We discuss the implications of these results to old Galactic neutron stars as sources of gamma-ray bursts.

Blaes, O. M.↗

Metallurgical processing in space

Research in metallurgical processing to study the effects of reduced gravity started with Apollo 14 and advanced with Skylab. Experiments provided specimens for analysis which solidified while constrained and while freely floating, which contained a mixture of normally immiscible materials, demonstrated enhanced capillary flow, solubility and ordered growth of a directionally solidified eutectic. The smaller, equiaxed grain structure obtained in reduced gravity compared to the larger, elongated grains obtained in one gravity indicate a difference in convection due to gravity in constrained solidification. Freely floating nickel alloy specimens showing metallic gas evolution at low pressure and reduced gravity suggest reduced pressure reactions which cannot occur on earth even in high vacuum chambers due to the hydrostatic head in the molten metal. Directionally solidified eutectics showed fewer termination defects when grown in reduced gravity. These are a few of the differences observed due to reduced gravity which could have important consequences on the future of metallurgy. In this paper we attempt to correlate the results of several Skylab solidification experiments.

Mckannan, E. C.↗

Transient nucleation in condensed systems

Using classical nucleation theory we consider transient nucleation occurring in a one-component, condensed system under isothermal conditions. We obtain an exact closed-form expression for the time dependent cluster populations. In addition, a more versatile approach is developed: a numerical simulation technique which models directly the reactions by which clusters are produced. This simulation demonstrates the evolution of cluster populations and nucleation rate in the transient regime. Results from the simulation are verified by comparison with exact analytical solutions for the steady state. Experimental methods for measuring transient nucleation are assessed, and it is demonstrated that the observed behavior depends on the method used. The effect of preexisting cluster distributions is studied. Previous analytical and numerical treatments of transient nucleation are compared to the solutions obtained from the simulation. The simple expressions of Kashchiev are shown to give good descriptions of the nucleation behavior.

Kelton, K. F.↗