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The isolation of three hydantoins from HCN oligomers is described. One of these hydantoins, 5-carboxymethylidine hydantoin (5-CMH), rearranges to pyrimidine orotic acid in basic solution. The isolation of 5-CMH suggests the possibility that pyrimidines were formed directly from HCN on the primitive earth.
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Dihydrouridine is absent from the tRNA of almost all hyperthermophiles and most Archaea but is ubiquitous in the tRNA of Eubacteria and Eukaryotes. In order to investigate whether this could be due to instability, the rate of ring opening of dihydrouridine was measured between 25 and 120 C. The dihydrouridine ring is stable at 25 C, but the half-life at 100 C and pH 7 is 9.1 h, which is comparable to the doubling time of hyperthermophiles. This suggests an explanation for the absence of dihydrouridine from the tRNA of hyperthermophiles. The rates of ring opening of dihydrouracil, dihydrothymine, and 1-N-methyldihydrouracil were measured at 100 C and pH 6-9, as were the equilibrium constants for ring closure of the ureido acids to the dihydrouracils. The pH rate profiles for ring opening and ring closing were calculated from the data. Possible roles for dihydrouracils in the pre-RNA world are discussed.
The reaction probabilities of N2O5 and ClONO2 with H2O on.
Simultaneous in situ measurements of stratospheric NO(sub 2), HNO(sub 3), HCI, and CH(sub 4) from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS)tunable diode laser spectrometer.
In the present paper, a report is presented on the effect of pH and carbonate on the hydrolysis rate constants of N-blocked and free aminoacyl adenylate anhydrides. Whereas the hydrolysis of free aminoacyl adenylates seems principally catalyzed by OH(-), the hydrolysis of the N-blocked species is also catalyzed by H(+), giving this compound a U-shaped hydrolysis vs. pH curve. Furthermore, at pH's less than 8, carbonate has an extreme catalytic effect on the hydrolysis of free aminoacyl-AMP anhydride, but essentially no effect on the hydrolysis of N-blocked aminoacyl-AMP anhydride. Furthermore, the N-blocked aminoacyl-AMP anhydride is a very efficient generator of peptides using free glycine as acceptor. The possible significance of the observations to prebiological peptide synthesis is discussed.
Selected imidazolide-activated nucleotides have been subjected to hydrolysis under conditions similar to those that favor their template-directed oligomerization. Rate constants of hydrolysis of the P-N bond in guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) and in guanosine 5'-monophosphate imidazolide (ImpG), kh, have been determined in the presence/absence of magnesium ion as a function of temperature and polycytidylate [poly(C)] concentration. Using the rate constant of hydrolysis of 2-MeImpG and the rate constant of elongation, i.e., the reaction of an oligoguanylate with 2-MeImpG in the presence of poly(C) acting as template, the limiting concentration of 2-MeImpG necessary for oligonucleotide elongation to compete with hydrolysis can be calculated. The limiting concentration is defined as the initial concentration of monomer that results in its equal consumption by hydrolysis and by elongation. These limiting concentrations of 2-MeImpG are found to be 1.7 mM at 37 degrees C and 0.36 mM at 1 degrees C. Boundary conditions in the form of limiting concentration of activated nucleotide may be used to evaluate a prebiotic model for chemical synthesis of biopolymers. For instance, the limiting concentration of monomer can be used as a basis of comparison among catalytic, but nonenzymatic, RNA-type systems. We also determined the rate constant of dimerization of 2-MeImpG, k2 = 0.45 +/- 0.06 M-1 h-1 in the absence of poly(C), and 0.45 +/- 0.06 less than or equal to k2 less than or equal to 0.97 +/- 0.13 M-1 h-1 in its presence at 37 degrees C and pH 7.95.(ABSTRACT TRUNCATED AT 250 WORDS).
Akaganeite (β-FeO(OH,Cl)) is a Fe(III) (hydr)oxide with a tunnel structure typically occupied by chloride. This mineral was first proposed to be present in Meridiani Planum and Gusev crater on Mars and akaganeite was subsequently detected by X-ray diffraction in Yellowknife Bay and Vera Rubin Ridge locations in Gale crater. Akaganeite in Gale crater has been proposed to form from Fe(II) sulfides but formation conditions remain unconstrained. We investigated akageneite formation by oxidative alteration of natural Fe(II) sulfide pyrrhotite exposed to HCl and oxidation-hydrolysis of Fe(II) HCl-leached from pyrrhotite at initial pH0 1.5, 2, 3, and 4. X-ray diffraction and Mössbauer analyses revealed formation of poorly-crystallized akageneite in oxidative alteration experiments. Air-exposure of the HCl-reacted dry pyrrhotite led to an increase in akageneite formation and precipitation of Fe(II) hydrated sulfates, goethite, and hydronium jarosite. Iron(II) oxidation-hydrolysis was sensitive to Si dissolved from phyllosilicates in one pyrrhotite sample. Akaganeite and goethite formed at pH0 1.5 and 2 with akageneite more abundant at dissolved Si/Fe ratio of 0.08 and goethite more abundant at Si/Fe of 0.01. Akaganeite formed together with hematite, ferrihydrite, and goethite at pH0 3, and formation was suppressed at pH0 4. Well-crystallized akageneite precipitated at pH0 1.5 while akaganeite of poorer crystallinity formed at pH0 2 and 3. Akageneite in Gale crater could form from sulfides by both mechanisms: oxidative alteration of sulfide minerals and oxidation-hydrolysis of leached Fe(II). The processes likely occurred during late diagenetic events triggered by interactions of acidic Cl-bearing groundwater with Fe(II) sulfides. Akaganeite in Yellowknife Bay, Gale crater could have formed by Fe(II) oxidation-hydrolysis either as a sole Fe(III) (hydr)oxide at pH<2 or along with ferrihydrite and hematite at 2<pH<4 in Si-enriched conditions. Akaganeite formation at Vera Rubin Ridge, Gale crater could have occurred through oxidative alteration of sulfides in Cl-bearing pH 1.2-1.5 solutions. The presence of well-crystalline akageneite in Vera Rubin Ridge indicates that Fe(II) oxidation-hydrolysis contributed to akageneite formation.
A nylon separator was placed in a flooded condition in K0H solution and heated at various high temperatures ranging from 60 C to 110 C. The weight decrease was measured and the molecular weight and decomposition product were analyzed to determine: (1) the effect of K0H concentration on the hydrolysis rate; (2) the effect of K0H concentration on nylon degradation; (3) the activation energy at different K0H concentrations; and (4) the effect of oxygen on nylon degradation. The nylon hydrolysis rate is shown to increase as K0H concentration is decreased 34%, giving a maximum rate at about 16%. Separator hydrolysis is confirmed by molecular weight decrease in age of the batteries, and the reaction of nylon with molecular oxygen is probably negligible, compared to hydrolysis. The extrapolated rate value from the high temperature experiment correlates well with experimental values at 35 degrees.
Compounds obtained by hydrolysis of HCN oligomers formed by allowing pH 9.2, 0.1 M cyanide to stand at room temperature for 4 to 12 months were analyzed. Hydrolysis of HCN oligomers yielded 4,5-dihydroxypyrimidine and 5-hydroxyuracil; orotic acid was detected after hydrolysis at pH 8.5. A unified pathway from diaminofumaronitrile to the pyrimidines observed is suggested. As purines, pyrimidines and amino acids are released by hydrolysis of HCN oligomers in either acidic or mildly basic aqueous solutions, they could have been formed on the primitive earth in spite of fluctuations in pH. 4,5-dihydroxypyrimidines appear to be likely candidates for incorporation into primitive nucleic acids, as they should undergo Watson-Crick hydrogen bonding with adenine.
A potential model is presented for the origin of optical activity in polypeptides on the primitive earth due to enantiomeric enrichment in succeeding polymerization-hydrolysis cycles. The model was developed in experiments with the polymerization of a DL-leucine N-carboxyanhydride mixture with a 31.2% enantiomeric excess of the L isomer with sodium methoxide initiator to yield a polyleucine product which was in turn partially hydrolyzed by acid. The polymerization-hydrolysis was found to produce a net 23.8% increase in the enantiomeric excess of the remaining unhydrolyzed polypeptide (14.2% from the polymerization and 9.6% from the partial hydrolysis). On the basis of these results, it is suggested that a slight excess produced by an appropriate chiral physical process may be enhanced by cycles of stereoselective polymerization and hydrolysis driven by fluctuating wet and dry environmental cycles on the primitive earth.
Studies of the properties of aminoacyl derivatives of 5'-AMP are aimed at understanding the origin of the process of protein synthesis. Aminoacyl (2',3') esters of 5'-AMP can serve as models of the 3'-terminus of aminoacyl tRNA. We report here on the relative rates of hydrolysis of Ac-D- and L-Phe AMP esters as a function of pH. At all pHs above 3, the rate constant of hydrolysis of the Ac-L-Phe ester is 1.7 to 2.1 times that of Ac-D-Phe ester. The D-isomer seems partially protected from hydrolysis by a stronger association with the adenine ring of the 5'-AMP.
Membranes from Halobacterium saccharovorum contained a cryptic ATPase which required Mg(2+) or Mn(2+) and was activated by Triton X-100. The optimal pH for ATP hydrolysis was 9-10. ATP or GTP were hydrolyzed at the same rate while ITP, CTP, and UTP were hydrolyzed at about half that rate. The products of ATP hydrolysis were ADP and phosphate. The ATPase required high concentrations (3.5 M) of NaCl for maximum activity. ADP was a competitive inhibitor of the activity, with an apparent Ki of 50 micro-M. Dicyclohexylcarbodiimide (DCCD) inhibited ATP hydrolysis. The inhibition was marginal at the optimum pH of the enzyme. When the ATPase was preincubated with DCCD at varying pH values, but assayed at the optimal pH for activity, DCCD inhibition was observed to increase with increasing acidity of the preincubation medium. DCCD inhibition was also dependent on time of preincubation, and protein and DCCD concentrations. When preincubated at pH 6.0 for 4 h at a protein:DCCD ratio of 40 (w/w), ATPase activity was inhibited 90 percent.
Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.
It is commonly assumed that template-directed polymerizations have played a key role in prebiotic evolution. A computer simulation that models up to 33 competing reactions was used to investigate the product distribution in a template-directed oligonucleotide synthesis as a function of time and concentration of the reactants. The study focuses on the poly(C)-directed elongation reaction of oligoguanylates, and how it is affected by the competing processes of hydrolysis and dimerization of the activated monomer, which have the potential of severely curtailing the elongation and reducing the size and yield of the synthesized polymers. The simulations show that realistic and probably prebiotically plausible conditions can be found where hydrolysis and dimerization are either negligible or where a high degree of polymerization can be attained even in the face of substantial hydrolysis and/or dimerization.
Biodegradation of plant biomass is a feasible path for transformation of crop residue and recycling of nutrients for crop growth. The need to model the effects of factors associated with recycling of plant biomass resulting from hydroponic sweet potato production has led to investigation of natural soil isolates with the capacity for starch hydrolysis. This study sought to use nondenaturing gel electrophoresis to characterize the proteins present in filtered effluent from bioreactors seeded with starch hydrolyzing bacterial culture used in the biodegradation of senesced sweet potato biomass. The study determined the relative molecular weight of proteins in sampled effluent and the protein banding pattern was characterized. The protein profiles of effluent were similar for samples taken from independent runs under similar conditions of starch hydrolysis. The method can be used as a quality control tool for confirmation of starch hydrolysis of crop biomass. In addition, this method will allow monitoring for presence of contaminants within the system-protein profiles indicative of new enzymes in the bioreactors.
On the path from inanimate to animate matter, a key step was the self-organization of molecules into protocells - the earliest ancestors of contemporary cells. Studies of the properties of protocells and the mechanisms by which they maintained themselves and reproduced are an important part of astrobiology. These studies also have the potential to greatly impact research in nanotechnology and computer science. Previous studies of protocells have focussed on self-replication. In these systems, Darwinian evolution occurs through a series of small alterations to functional molecules whose identities are stored. Protocells, however, may have been incapable of such storage. We hypothesize that under such conditions, the replication of functions and their interrelationships, rather than the precise identities of the functional molecules, is sufficient for survival and evolution. This process is called non-genomic evolution. Recent breakthroughs in experimental protein chemistry have opened the gates for experimental tests of non-genomic evolution. On the basis of these achievements, we have developed a stochastic model for examining the evolutionary potential of non-genomic systems. In this model, the formation and destruction (hydrolysis) of bonds joining amino acids in proteins occur through catalyzed, albeit possibly inefficient, pathways. Each protein can act as a substrate for polymerization or hydrolysis, or as a catalyst of these chemical reactions. When a protein is hydrolyzed to form two new proteins, or two proteins are joined into a single protein, the catalytic abilities of the product proteins are related to the catalytic abilities of the reactants. We will demonstrate that the catalytic capabilities of such a system can increase. Its evolutionary potential is dependent upon the competition between the formation of bond-forming and bond-cutting catalysts. The degree to which hydrolysis preferentially affects bonds in less efficient, and therefore less well-ordered, peptides is also critical to evolution of a non-genomic system. Based on these results, a new computational object called a "molnet" is defined. Like a neural network, it is formed of interconnected units that send "signals" to each other. Like molecules, neural networks have a specific function once their structure is defined. The difference between a molnet and traditional neural networks, is that input to molnets is not simply passed along and processed from input to output units, but rather it is utilized to form and break connections(bonds), and thus to form new structures. Molnets represent a powerful tool that can be used to understand the conditions under which chemical systems can form large molecules, such as proteins, and display ever more complex functions. This has direct applications, for example to the design of smart,synthetic fabrics. Additional information is contained in the original.