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At least 307 records · Page 17

The prebiotic chemistry of nucleotides

Diminosuccinonitrile (DISN), formed by the oxidation of diaminomaleonitrile, has been investigated as a potential prebiotic phosphorylating agent. DISN affects the cyclization of 3'-adenosine monophosphate to adenosine 2',3'-cyclic phosphate in up to 39 percent yield. The mechanism of this reaction was investigated. The DISN-mediated phosphorylation of uridine to uridine monophosphate does not proceed efficiencly in aqueous solution. The reaction of DISN with uridine-5'-phosphate and uridine results in the formation of 2,2'-anhydronucleotides and 2,2'-anhydronucleosides respectively, and other reaction products resulting from an initial reaction at the 2'- and 3'-hydroxyl groups. The clay mineral catalysis of the cyclization of adenosine-3'-phosphate was investigated using homoionic montmorillonites.

Ferris, J. P.↗

Nonenzymatic formation of 'energy-rich' lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol

The energy rich thioester, N-acetyl-S-lactoylcysteine, is formed under anaerobic conditions from glyceraldehyde and N-acetylcysteine at ambient temperature in aqueous solutions of sodium phosphate (pH 7.0). The conversion occurs at a rate of about 0.4 percent per day in reactions with 10 millimoles (mM) glyceraldehyde, 40 mM thiol, and 500 mM sodium phosphate (pH 7.0). Thioester formation proceeds at an estimated efficiency of 76 percent. The formation of lactoyl thioester most likely occurs by the phosphate catalyzed dehydration of glyceraldehyde to give pyruvaldehyde, which combines with thiol to form a hemithioacetal that rearranges to the thioester. A second energy rich thioester, N-acetyl-S-glyceroylcysteine, is also produced from glyceraldehyde when these reactions are carried out in the presence of oxygen and to a limited extent in the absence of oxygen. In the presence of oxygen, the formation of glyceroyl thioester continues until the thiol disappears completely by oxidation. The significance of these reactions to the energetics of the origin of life is discussed.

Weber, A. L.↗

Project Explorer

PROJECT EXPLORER is a program that will fly student-developed experiments onboard the Space Shuttle in NASA's Get-Away Special (GAS) containers. The program is co-sponsored by the Alabama Space and Rocket Center, the Alabama-Mississippi Section of the American Institute of Aeronautics and Astronautics, Alabama A&M University and requires extensive support by the University of Alabama in Huntsville. A unique feature of this project will demonstrate transmissions to ground stations on amateur radio frequencies in English language. Experiments Nos. 1, 2, and 3 use the microgravity of space flight to study the solidification of lead-antimony and aluminum-copper alloys, the growth of potassium-tetracyanoplatinate hydrate crystals in an aqueous solution, and the germination of radish seeds. Flight results will be compared with Earth-based data. Experiment No. 4 features radio transmission and will also provide timing for the start of all other experiments. A microprocessor will obtain real-time data from all experiments as well as temperature and pressure measurements taken inside the canister. These data will be transmitted on previously announced amateur radio frequencies after they have been converted into the English language by a digitalker for general reception.

Dannenberg, K. K.↗

Hydrothermal alteration of CM carbonaceous chondrites: Implications of the identification of tochilinite as one type of meteoritic PCP

Poorly characterized phases (PCP's) constitute up to 30 volume percent of some CM carbonaceous chondrites, and are therefore an important key to an understanding of the physico-chemical conditions attending matrix evolution. An iron rich form of the terrestrial phase tochilinite was recently identified as a common type of PCP. Tochilinite has the general formula 6Fe(0.9)S.5(Mg,Fe)(OH)2 and consists of alternating machinawite (FeS) and brucite ((Mg,Fe)(OH)2) sheets, with iron vacancies in the sulfide sheets. In iron rich tochilinite, ferrous hydroxide, called amakinite, replaces brucite. If CM carbonaceous kchondrites have underdone hydrothermal alteration, iron rich tochilinite, at least, probably grew from aqueous solutions characterized by low FO2, high FS2, pH 10 to 12, and at a temperature at or below 170 C.

Zolensky, M. E.↗

Production method of nickel electrode

A nickel electrode having improved charging efficiency, an increased coefficient of discharging utilization, and large capacity is disclosed. Nickel hydroxide or nickel oxide is retained in a porous nickel substrate which is immersed in an aqueous solution of cobalt acetate with a pH 4.0 to 6.8. The electrode thus obtained is then immersed in an alkaline solution or heated to change cobalt acetate into cobalt hydroxide or cobalt oxide whereby the surface of nickel active material is covered with cobalt crystals and alloying of cobalt and nickel is promoted at the same time.

Ikeda, H.↗

Method of producing nickel electrode

A large capacity nickel electrode is provided in which the charging efficiency and discharge utilization coefficient are improved in comparison to nickel electrodes which are produced by the conventional method. Nickel electrodes retaining nickel active material or nickel active material and cobalt compounds on a porous nickel substrate are immersed in a cobalt sulfate aqueous solution whose pH is adjusted in the range of 3.5 to 6.0, followed by crystallization of the hydroxide or oxide by pyrolysis or immersion in alkali, thereby coating the surface of the nickel active material with cobalt crystals and simultaneously promoting alloying of the nickel-cobalt.

Ikeda, Y.↗

Prebiotic formation of 'energy-rich' thioesters from glyceraldehyde and N-acetylcysteine

The 'energy-rich' thioester, N-acetyl-S-lactoylcysteine, is formed from low concentrations of glyceraldehyde and N-acetylcysteine under anaerobic conditions at ambient temperature in aqueous solutions of sodium phosphate (pH 7.0). Reactions with 2mM glyceraldehyde, 2mM N-acetylcysteine, and 500 mM sodium phosphate (pH 7.0) convert about 0.3 percent/day of the glyceraldehyde to lactoyl thioester. The formation of lactoyl thioester in similar reactions with 500 mM imidazole hydrochloride (pH 7.0) is supported by the thiol-dependence of lactate formation, which is 3-fold greater in the presence of thiol (0.11 percent/day) than in the absence of thiol (0.04 percent/day). The formation of lactoly thioester is thought to proceed by the phosphate (or imidazole)-catalyzed dehydration of glyceraldehyde, which adds to the thiol to form a hemithioacetal that rearranges to the thioester. A limited amount of a second thioester, N-acetyl-S-glyceroyl-cysteine, is also formed at the beginning of these reactions. The significance of these reactions to the origin of life is discussed.

Weber, A. L.↗

A potentiodynamic study of aluminum-lithium alloys in an aqueous sodium chloride environment

The characteristics of the potentiodynamic curves for Al-Li alloys in 3.5 percent NaCl aqueous solution are explained and the electrochemical parameters of the potentiodynamic technique are correlated to observed pitting and intergranular cracking behavior. It is shown that the oxygen content of the sodium chloride electrolyte plays an important role in the electrochemical behavior of Al-Li alloys. The potentiodynamic behavior of the alloys is found to be insensitive to variation in compositional content and heat treatment, both of which affect the stress-corrosion behavior. Stringer oxide particle attack and random pitting are observed. It is shown that alternate-immersion exposure prior to potentiodynamic polarization may offer a means of assessing susceptibility to stress-corrosion cracking.

Tsao, C.-H. T.↗

Prebiotic syntheses of purines and pyrimidines

The results of experimental and theoretical investigations of the prebiotic synthesis of purines and pyramidines are surveyed. Topics examined include the synthesis of purines from HCN via 4,5-disubstituted imidazole derivatives in aqueous solutions or liquid NH3, simultaneous formation of amino acids and purines by electron irradiation of CH4-NH3-H2O mixtures, synthesis of pyrimadines from cynoacetylene, energetics, formation of bases under anhydrous or concentrated conditions, formation of bases under dilute conditions, Fischer-Tropsch-type reactions, and the role of activated intermediates. It is pointed out that the precursor compounds have been detected in the interstellar medium, on Titan, and in other solar-system bodies, and that solar-nebula HCN concentrations of the order of 1-10 mM have been estimated on the basis of meteorite measurements.

Basile, B.↗

New Instrumentation for Phase Partitioning

Cells and molecules can be purified by partitioning between the two immiscible liquid phases formed by aqueous solutions of poly/ethylene glycol and dextran. Such purification can be more selective, higher yielding, and less destructive to sensitive biological materials than other available techniques. Earth's gravitational field is a hindering factor as it causes sedimentation of particles to be purified and shear-induced particle randomization. The present proposal is directed toward developing new instrumentation for performing phase partitioning both on Earth and in microgravity.

Harris, J. M.↗

Rationale for two phase polymer system microgravity separation experiments

The two-phase systems that result when aqueous solutions of dextran and poly(ethylene glycol) are mixed at concentrations above a few percent are discussed. They provide useful media for the partition and isolation of macromolecules and cell subpopulations. By manipulating their composition, separations based on a variety of molecular and surface properties are achieved, including membrane hydrophobic properties, cell surface charge, and membrane antigenicity. Work on the mechanism of cell partition shows there is a randomizing, nonthermal energy present which reduces separation resolution. This stochastic energy is probably associated with hydrodynamic interactions present during separation. Because such factors should be markedly reduced in microgravity, a series of shuttle experiments to indicate approaches to increasing the resolution of the procedure are planned.

Brooks, D. E.↗

Lightweight nickel electrode for nickel hydrogen cells and batteries

The nickel electrode was identified as the heaviest component of the nickel hydrogen (NiH2) battery. The NASA Lewis Research Center is developing nickel electrodes for NiH2 battery devices which will be lighter in weight and have higher energy densities when cycled under a low Earth orbit regime at deep depths of discharge. Lightweight plaques are first exposed to 31 percent potassium hydroxide for 3 months to determine their suitability for use as electrode substrates from a chemical corrosion standpoint. Pore size distribution and porosity of the plaques are then measured. The lightweight plaques examined are nickel foam, nickel felt, nickel plastic and nickel plated graphite. Plaques are then electrochemically impregnated in an aqueous solution. Initial characterization tests of the impregnated plaques are performed at five discharge levels, C/2, 1.0 C, 1.37 C, 2.0C, and 2.74 C rates. Electrodes that passed the initial characterization screening test will be life cycle tested. Lightweight electrodes are approximately 30 to 50 percent lighter in weight than the sintered nickel electrode.

Britton, D. L.↗

Intramolecular interactions in aminoacyl nucleotides: Implications regarding the origin of genetic coding and protein synthesis

Cellular organisms store information as sequences of nucleotides in double stranded DNA. This information is useless unless it can be converted into the active molecular species, protein. This is done in contemporary creatures first by transcription of one strand to give a complementary strand of mRNA. The sequence of nucleotides is then translated into a specific sequence of amino acids in a protein. Translation is made possible by a genetic coding system in which a sequence of three nucleotides codes for a specific amino acid. The origin and evolution of any chemical system can be understood through elucidation of the properties of the chemical entities which make up the system. There is an underlying logic to the coding system revealed by a correlation of the hydrophobicities of amino acids and their anticodonic nucleotides (i.e., the complement of the codon). Its importance lies in the fact that every amino acid going into protein synthesis must first be activated. This is universally accomplished with ATP. Past studies have concentrated on the chemistry of the adenylates, but more recently we have found, through the use of NMR, that we can observe intramolecular interactions even at low concentrations, between amino acid side chains and nucleotide base rings in these adenylates. The use of this type of compound thus affords a novel way of elucidating the manner in which amino acids and nucleotides interact with each other. In aqueous solution, when a hydrophobic amino acid is attached to the most hydrophobic nucleotide, AMP, a hydrophobic interaction takes place between the amino acid side chain and the adenine ring. The studies to be reported concern these hydrophobic interactions.

Lacey, J. C., Jr.↗

Biosynthetic Porphyrins and the Origin of Photosynthesis

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

David Mauzerall↗

Acrolein Microspheres Are Bonded To Large-Area Substrates

Reactive cross-linked microspheres produced under influence of ionizing radiation in aqueous solutions of unsaturated aldehydes, such as acrolein, with sodium dodecyl sulfate. Diameters of spheres depend on concentrations of ingredients. If polystyrene, polymethylmethacrylate, or polypropylene object immersed in solution during irradiation, microspheres become attached to surface. Resulting modified surface has grainy coating with reactivity similar to free microspheres. Aldehyde-substituted-functional microspheres react under mild conditions with number of organic reagents and with most proteins. Microsphere-coated macrospheres or films used to immobilize high concentrations of proteins, enzymes, hormones, viruses, cells, and large number of organic compounds. Applications include separation techniques, clinical diagnostic tests, catalytic processes, and battery separators.

Rembaum, Alan↗

Protein-crystal growth experiment (planned)

To evaluate the effectiveness of a microgravity environment on protein crystal growth, a system was developed using 5 cubic feet Get Away Special payload canister. In the experiment, protein (myoglobin) will be simultaneously crystallized from an aqueous solution in 16 crystallization units using three types of crystallization methods, i.e., batch, vapor diffusion, and free interface diffusion. Each unit has two compartments: one for the protein solution and the other for the ammonium sulfate solution. Compartments are separated by thick acrylic or thin stainless steel plates. Crystallization will be started by sliding out the plates, then will be periodically recorded up to 120 hours by a still camera. The temperature will be passively controlled by a phase transition thermal storage component and recorded in IC memory throughout the experiment. Microgravity environment can then be evaluated for protein crystal growth by comparing crystallization in space with that on Earth.

Fujita, S.↗

Demixing of aqueous polymer two-phase systems in low gravity

When polymers such as dextran and poly(ethylene glycol) are mixed in aqueous solution biphasic systems often form. On Earth the emulsion formed by mixing the phases rapidly demixes because of phase density differences. Biological materials can be purified by selective partitioning between the phases. In the case of cells and other particulates the efficiency of these separations appears to be somewhat compromised by the demixing process. To modify this process and to evaluate the potential of two-phase partitioning in space, experiments on the effects of gravity on phase emulsion demixing were undertaken. The behavior of phase systems with essentially identical phase densities was studied at one-g and during low-g parabolic aircraft maneuvers. The results indicate the demixing can occur rather rapidly in space, although more slowly than on Earth. The demixing process was examined from a theoretical standpoint by applying the theory of Ostwald ripening. This theory predicts demizing rates many orders of magnitude lower than observed. Other possible demixing mechanisms are considered.

Bamberger, S.↗

Growth kinetics of the (001) face of TGS below the ferroelectric transition temperature

The growth rates of the (001) face of triglycine sulfate (TGS) from aqueous solutions were measured at 33.55 C in an apparatus which produced a laminar flow of solution past the crystal. The data of growth rate as a function of relative supersaturation were compared with the results of two well-known models: the Burton-Cabrera-Frank (1951) surface diffusion model and the birth-and-spreading growth model. Both models produced good fits to the growth rate data. However, on the basis of the qualitative aspects of the experimentally-observed growth, it is suggested that the correct growth model for these crystals is the Burton-Cabrera-Frank model.

Reiss, D. A.↗