Nonradiative transfer of excitation energy between rare-earth ions in aqueous solution.
Nonradiative transfer of excitation energy between mixed trinuclear complexes of Tb and Eu ions with lactose in aqueous solution
Quiring, F. S.↗
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Photochemical determination of oxalate.
Oxalate determination in two methods based on photochemical decomposition of ferric oxalate complexes in aqueous acidic solution
PHOTOCHEMICAL REACTION↗
Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3)
A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.
Sheridan, P. S.↗
RIO Tinto Faulted Volcanosedimentary Deposits as Analog Habitats for Extant Subsurface Biospheres on Mars: A Synthesis of the MARTE Drilling Project Geobiology Results
Geochemistry and mineralogy on Mars surface characterized by the MER Opportunity Rover suggest that early Mars hosted acidic environments in the Meridiani Planum region [1, 2]. Such extreme paleoenvironments have been suggested to be a regional expression of the global Mars geological cycle that induced acidic conditions by sulfur complexation and iron buffering of aqueous solutions [3]. Under these assumptions, underground reservoirs of acidic brines and, thereby, putative acidic cryptobiospheres, may be expected. The MARTE project [4, 5] has performed a drilling campaign to search for acidic and anaerobic biospheres in R o Tinto basement [6] that may be analogs of these hypothetical communities occurring in cryptic habitats of Mars. This Rio Tinto geological region is characterized by the occurrence of huge metallic deposits of iron sulfides [7]. Late intensive diagenesis of rocks driven by a compressive regimen [8] largely reduced the porosity of rocks and induced a cortical thickening through thrusting and inverse faulting and folding. Such structures play an essential role in transporting and storing water underground as any other aquifers do in the Earth. Once the underground water reservoirs of the Ro Tinto basement contact the hydrothermal pyrite deposits, acidic brines are produced by the release of sulfates and iron through the oxidation of sulfides [9].
Fernandez-Remolar, D. C.↗
Flame-Retardant Diaminobenzenes Containing Phosphorus
Diamines polymerized with dianhydrides or diacyl halides to produce fire-resistant polymers. Properties of polymers useful as matrices in laminated composite-material aircraft structural components that resist fire and exhibit desirable mechanical properties as high tensile strength. Diamines used as encapsulating or potting compounds when reacted with epoxy resins. Free phosphonic acids, byproducts of synthesis of diamines used as complexing agents to extract metals from aqueous solutions or as corrosion inhibitors for metals.
Kourtides, Demetrius A.↗
Analysis of gas absorption to a thin liquid film in the presence of a zero-order chemical reaction
The paper presents a detailed theoretical analysis of the process of gas absorption to a thin liquid film adjacent to a horizontal rotating disk. The film is formed by the impingement of a controlled liquid jet at the center of the disk and subsequent radial spreading of liquid along the disk. The chemical reaction between the gas and the liquid film can be expressed as a zero-order homogeneous reaction. The process was modeled by establishing equations for the conservation of mass, momentum, and species concentration and solving them analytically. A scaling analysis was used to determine dominant transport processes. Appropriate boundary conditions were used to solve these equations to develop expressions for the local concentration of gas across the thickness of the film and distributions of film height, bulk concentration, and Sherwood number along the radius of the disk. The partial differential equation for species concentration was solved using the separation of variables technique along with the Duhamel's theorem and the final analytical solution was expressed using confluent hypergeometric functions. Tables for eigenvalues and eigenfunctions are presented for a number of reaction rate constants. A parametric study was performed using Reynolds number, Ekman number, and dimensionless reaction rate as parameters. At all radial locations, Sherwood number increased with Reynolds number (flow rate) as well as Ekman number (rate of rotation). The enhancement of mass transfer due to chemical reaction was found to be small when compared to the case of no reaction (pure absorption), but the enhancement factor was very significant when compared to pure absorption in a stagnant liquid film. The zero-order reaction processes considered in the present investigation included the absorption of oxygen in aqueous alkaline solutions of sodiumdithionite and rhodium complex catalyzed carbonylation of methanol. Present analytical results were compared to previous theoretical results for limiting conditions, and were found to have very good agreement.
Rajagopalan, S.↗
Nonbiological fractionation of iron isotopes
Laboratory experiments demonstrate that iron isotopes can be chemically fractionated in the absence of biology. Isotopic variations comparable to those seen during microbially mediated reduction of ferrihydrite are observed. Fractionation may occur in aqueous solution during equilibration between inorganic iron complexes. These findings provide insight into the mechanisms of iron isotope fractionation and suggest that nonbiological processes may contribute to iron isotope variations observed in sediments.
NASA Discipline Exobiology↗
The assembly and properties of protobiological structures - The beginnings of cellular peptide synthesis
New data indicate that lysine-rich proteinoids have the ability to catalyze the synthesis of peptide bonds from a variety of amino acids and ATP. This capacity is evident in aqueous solution, in suspension of phase-separated complexes of lysine-rich proteinoid with acidic proteinoids, and in suspension of phase-separated particles composed of lysine-rich proteinoids with polynucleotides. Since the proteinoid complexes can contain other catalytic activities, including ability to catalyze internucleotide bond formation, it is inferred that the first protocells on earth already had a number of biological types of activity.
Fox, S. W.↗
Growth from Solutions: Kink dynamics, Stoichiometry, Face Kinetics and stability in turbulent flow
1. Kink dynamics. The first segment of a polygomized dislocation spiral step measured by AFM demonstrates up to 60% scattering in the critical length l*- the length when the segment starts to propagate. On orthorhombic lysozyme, this length is shorter than that the observed interkink distance. Step energy from the critical segment length based on the Gibbs-Thomson law (GTL), l* = 20(omega)alpha/(Delta)mu is several times larger than the energy from 2D nucleation rate. Here o is tine building block specific voiume, a is the step riser specific free energy, Delta(mu) is the crystallization driving force. These new data support our earlier assumption that the classical Frenkel, Burton -Cabrera-Frank concept of the abundant kink supply by fluctuations is not applicable for strongly polygonized steps. Step rate measurements on brushite confirms that statement. This is the1D nucleation of kinks that control step propagation. The GTL is valid only if l* <Dk/vk, the diffusion path of a kink that has diffusivity Dk and average growth velocity vk. This is equivalent to supersaturations sigma less than approx. alpha/2l*, where alpha is the building block size. For lysozyme, sigma much less than (1%). Conventionally used interstep distance generated by screw dislocation, 19(omega)alpha/Delta(mu) should be replaced by the very different real one, approx.4l*. 2. Stoichiometry. Kink, and thus step and face rates of a non-Kossel complex molecular monocomponent or any binary, AB, lattice was found theoretically to be proportional to 1/(zeta(sup 1/2) + zeta(sup - 1/2)), where zeta = [B]/[A] is the stoichiometry ratio in solution. The velocities reach maxima at zeta = 1. AFM studies of step rates on CaOxalate monohydrate (kidney stones) from aqueous solution was found to obey the law mentioned above. Generalization for more complex lattice will be discussed. 3. Turbulence. In agreement with theory, high precision in-situ laser interferometry of the (101) KDP crystal face shows step bunching if solution flows parallel to the step flow. The bunch height increases with the distance the bunch travels, i.e. with the face size. However, when the flow rate, u, increases, at u greater than approx. 1 m / s , the average step bunch height decreases as 1/u. The pheonomenon is attributed to the turbulent rather than laminar viscous boundary layer where diffusivity Dt = 0.5u(sub tau),y, i.e. increases linearly with the distance y from the solid face. Friction velocity, u(sub tau) approx. u(sup 7/8). Dramatically larger rate of the mass/heat transport within the turbulent, as compared to the laminar, viscous layer will be discussed.
Chernov, A. A.↗
Oxidative peptide /and amide/ formation from Schiff base complexes
One hypothesis of the origin of pre-modern forms of life is that the original replicating molecules were specific polypeptides which acted as templates for the assembly of poly-Schiff bases complementary to the template, and that these polymers were then oxidized to peptide linkages, probably by photo-produced oxidants. A double cycle of such anti-parallel complementary replication would yield the original peptide polymer. If this model were valid, the Schiff base between an N-acyl alpha mino aldehyde and an amino acid should yield a dipeptide in aqueous solution in the presence of an appropriate oxidant. In the present study it is shown that the substituted dipeptide, N-acetyl-tyrosyl-tyrosine, is produced in high yield in aqueous solution at pH 9 through the action of H2O2 on the Schiff-base complex between N-acetyl-tyrosinal and tyrosine and that a great variety of N-acyl amino acids are formed from amino acids and aliphatic aldehydes under similar conditions.
Strehler, B. L.↗
Computer modeling of the mineralogy of the Martian surface, as modified by aqueous alteration
Mineralogical constraints can be placed on the Martian surface by assuming chemical equilibria among the surface rocks, atmosphere and hypothesized percolating groundwater. A study was made of possible Martian surface mineralogy, as modified by the action of aqueous alteration, using the EQ3/6 computer codes. These codes calculate gas fugacities, aqueous speciation, ionic strength, pH, Eh and concentration and degree of mineral saturation for complex aqueous systems. Thus, these codes are also able to consider mineralogical solid solutions. These codes are able to predict the likely alteration phases which will occur as the result of weathering on the Martian surface. Knowledge of the stability conditions of these phases will then assist in the definition of the specifications for the sample canister of the proposed Martian sample return mission. The model and its results are discussed.
Zolensky, M. E.↗
Additional studies for the spectrophotometric measurement of iodine in water
Previous work in iodine spectroscopy is briefly reviewed. Continued studies of the direct spectrophotometric determination of aqueous iodine complexed with potassium iodide show that free iodine is optimally determined at the isosbestic point for these solutions. The effects on iodine determinations of turbidity and chemical substances (in trace amounts) is discussed and illustrated. At the levels tested, iodine measurements are not significantly altered by such substances. A preliminary design for an on-line, automated iodine monitor with eventual capability of operating also as a controller was analyzed and developed in detail with respect single beam colorimeter operating at two wavelengths (using a rotating filter wheel). A flow-through sample cell allows the instrument to operate continuously, except for momentary stop flow when measurements are made. The timed automatic cycling of the system may be interrupted whenever desired, for manual operation. An analog output signal permits controlling an iodine generator.
Source record↗
The SNC Meteorites Are From Mars
The thirteen SNC meteorites are all igneous rocks, either basalts or basaltic cumulates. They are inferred to be from Mars, based on direct comparison with martian materials and on consistency with inferences about Mars. Most telling is that the SNC meteorites contain traces of gas which is very similar in elemental and isotopic compositions to the modem Martian atmosphere as measured by Viking. The martian atmosphere appears to be unique in the solar system, so its presence in the SNCs is accepted as virtually unequivocal proof that they formed on Mars. Independent of this link, the SNC meteorites must be from a planet with a significant atmosphere because they contain several abundant gas components, some of which carry large isotopic fractionations characteristic of atmospheric processing. The chemical compositions of the SNC meteorites are also consistent with data from in situ analyses of martian soils and rocks, and are quite different from compositions of other meteorites, rocks from the Earth, and rocks from the Moon. The range of formation ages for the SNC meteorites, 4.5 Ga to 0. 18 Ga, is consistent with the varied ages of the Martian surface (based on its cratering record) and inconsistent with surface ages on any other solar system body. The extreme chemical fractionations in the SNC meteorites suggest complex internal processes on a large planet, which is inconsistent with an asteroidal origin. Some SNCs were altered by aqueous solutions at greater than 0.7 Ga, consistent with the recent presence of liquid groundwater in Mars inferred independently from the geology of its surface. There seems little likelihood that the SNCs are not from Mars. If they were from another planetary body, it would have to be substantially identical to Mars as it now is understood.
Treiman, Allan H.↗
Is Water Necessary for Life?
The universality of water as the solvent for life is usually justified by its role in supporting the rich organic chemistry. It has been pointed out, however, that even richer synthetic chemistry is possible in other organic solvents. Does it mean that water is not necessary for life? Here, other, essential criteria for solvent for life that have not been sufficiently considered are discussed. In biological systems, complex molecules are not only constantly synthesized but also degraded. Solvent-mediated degradation is essential for regulating cell content, preventing overcrowding and allowing for recycling organic material. Achieving a balance between synthetic and degradative processes is facile in water, but not in many other organic liquids. Thus, the so-called “water paradox” according to which water is both necessary to life and toxic to biopolymer synthesis might not be paradoxical at all. The machinery of life is based on non-covalent interactions that do not involve making or breaking chemical bonds. Their strength needs to be properly tuned. If they are too weak, there might be undesired response to natural fluctuations of physical or chemical parameters. If they are too strong, the kinetics and energetics of cellular processes could adversely influenced. The solvent must allow for balancing these interactions, which provides strong, universal constraints on the medium for life. Water influences non-covalent interactions mainly by two mechanisms. First, it reduces strong, electrostatic interactions between molecules, chemical groups or atoms carrying electric charge or dipole. Second, it induces the hydrophobic effect, the tendency to remove non-polar (hydrophobic) molecules and groups from direct contact with aqueous solution and, instead, interact with each other. In living systems, the hydrophobic effect is largely responsible for self-organization of molecules to more complex structures, such as aggregation of lipid molecules to form biological membranes and protein folding. Water exists as stable liquid in a large temperature range, and the hydrophobic effects are a consequence of the temperature insensitivity of essential properties of its liquid state. In summary, water accomplishes an amazing feat – it reduces strong interactions between dissolved species and simultaneously increases the strength of weak interactions, bringing all of them to the right range. Once we consider not only synthetic capabilities but also other required traits of the solvent for life, no viable alternative to water is currently known.
Life↗
Studies related to primitive chemistry. A proton and nitrogen-14 nuclear magnetic resonance amino acid and nucleic acid constituents and a and their possible relation to prebiotic
Preliminary proton nuclear magnetic resonance (NMR) studies were made to determine the applicability of this technique for the study of interactions between monomeric and polymeric amino acids with monomeric nucleic acid bases and nucleotides. Proton NMR results for aqueous solutions (D2O) demonstrated interactions between the bases cytosine and adenine and acidic and aromatic amino acids. Solutions of 5'-AMP admixed with amino acids exhibited more complex behavior but stacking between aromatic rings and destacking at high amino acids concentration was evident. The multisite nature of 5'-AMP was pointed out. Chemical shift changes for adenine and 5'-AMP with three water soluble polypeptides demonstrated that significant interactions exist. It was found that the linewidth-pH profile of each amino acid is unique. It is concluded that NMR techniques can give significant and quantitative data on the association of amino acid and nucleic acid constituents.
Manatt, S. L.↗
Structure of an anti-HIV-1 hammerhead ribozyme complex with a 17-mer DNA substrate analog of HIV-1 gag RNA and a mechanism for the cleavage reaction: 750 MHz NMR and computer experiments
The structure of an anti-HIV-1 ribozyme-DNA abortive substrate complex was investigated by 750 MHz NMR and computer modeling experiments. The ribozyme was a chimeric molecule with 30 residues-18 DNA nucleotides, and 12 RNA residues in the conserved core. The DNA substrate analog had 17 residues. The chimeric ribozyme and the DNA substrate formed a shortened ribozyme-abortive substrate complex of 47 nucleotides with two DNA stems (stems I and III) and a loop consisting of the conserved core residues. Circular dichroism spectra showed that the DNA stems assume A-family conformation at the NMR concentration and a temperature of 15 degrees C, contrary to the conventional wisdom that DNA duplexes in aqueous solution populate entirely in the B-form. It is proposed that the A-family RNA residues at the core expand the A-family initiated at the core into the DNA stems because of the large free energy requirement for the formation of A/B junctions. Assignments of the base H8/H6 protons and H1' of the 47 residues were made by a NOESY walk. In addition to the methyl groups of all T's, the imino resonances of stems I and III and AH2's were assigned from appropriate NOESY walks. The extracted NMR data along with available crystallographic data, were used to derive a structural model of the complex. Stems I and III of the final model displayed a remarkable similarity to the A form of DNA; in stem III, a GC base pair was found to be moving into the floor of the minor groove defined by flanking AT pairs; data suggest the formation of a buckled rhombic structure with the adjacent pair; in addition, the base pair at the interface of stem III and the loop region displayed deformed geometry. The loop with the catalytic core, and the immediate region of the stems displayed conformational multiplicity within the NMR time scale. A catalytic mechanism for ribozyme action based on the derived structure, and consistent with biochemical data in the literature, is proposed. The complex between the anti HIV-1 gag ribozyme and its abortive DNA substrate manifests in the detection of a continuous track of A.T base pairs; this suggests that the interaction between the ribozyme and its DNA substrate is stronger than the one observed in the case of the free ribozyme where the bases in stem I and stem III regions interact strongly with the ribozyme core region (Sarma, R. H., et al. FEBS Letters 375, 317-23, 1995). The complex formation provides certain guidelines in the design of suitable therapeutic ribozymes. If the residues in the ribozyme stem regions interact with the conserved core, it may either prevent or interfere with the formation of a catalytically active tertiary structure.
NASA Discipline Exobiology↗
Characterization of soil and postlaunch pad debris from Cape Canaveral launch complex and analysis of soil interaction with aqueous HCl
Soil samples were fractionated and analyzed in order to assess the physical and chemical interactions of entrained soil with solid-rocket exhaust clouds. The sandy soil consisted primarily of quartz (silica) particles, 30 to 500 microns in diameter, and also contained seashell fragments. Differential and cumulative soil-mass size distributions are presented along with mineralogy, elemental compositions, and solution pH histories. About 90 percent of the soil mass consisted of particles 165 microns in diameter. Characteristic reaction times in aqueous HC1 slurries varied from a few minutes to several days, and capacities for reaction under acidic conditions varied from 10 to 40 g HCl/kg soil, depending on particle size. Airborne lifetimes of particles 165 microns are conservatively 30 min, and this major grouping is predicted to represent a small short-term chemical sink for up to 5% of the total HC1. The smaller and more minor fractions, below a 165 micron diameter, may act as giant cloud condensation nuclei over much longer airborne lifetimes. Finally, the demonstrated time dependency of neutralization is a complicating factor; it can influence the ability to deduce in-cloud HCl scavenging with reaction and can affect the accuracy of measured chemical compositions of near-field wet deposition.
Pellett, G. L.↗
Method and apparatus for hydrogen production from water
A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.
Muradov, Nazim Z.↗