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At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Engineering uranyl-chelating peptides from NikR for electrochemical peptide-based sensing applications

We have, for the first time, designed three uranyl-chelating peptides by modeling after the uranyl binding pocket found in a mutated Ni(II)-dependent transcriptional repressor (NikR). All three thiolated and methylene blue (MB)-modified peptides, NikR-5, NikR-11, and NikR-15, contain the five core amino acids responsible for target recognition, but the two longer peptides have either one or two additional glycine residues in between the five amino acids. These three peptide probes were then used in the fabrication of electrochemical peptide-based (E-PB) uranyl ion (U(VI)) sensors, with the goal of elucidating the effects of the added glycine residues and probe flexibility on target recognition. The sensing mechanism is similar to other “signal-off” E-PB sensors, in which binding of the target rigidifies the probe, resulting in a decrease in the redox signal from the tethered MB label. Although all three sensors responded to U(VI), the NikR-15 sensor's behavior was irreproducible and thus precluded from the rest of the study. The NikR-11 sensor showed the largest response to U(VI), whereas the NikR-5 sensor showed higher specificity for U(VI). The limit of detection was 50 nM for both sensors, which is well below the U.S. Environmental Protection Agency maximum contaminant level for uranium. Both sensors were further tested and proven functional in a 50% synthetic aquifer sample. Overall, the NikR-11 sensor, fabricated with the 11-amino acid probe, is deemed the optimal design. Incorporating glycine residues is a strategic way to lengthen the peptide slightly to improve target binding. This simple yet versatile approach to recreating binding pockets on electrode surfaces can potentially be employed in the design of other E-PB and surface-based metal ion sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Isolation of Purines and Pyrimidines from the Murchison Meteorite

The origin of life on Earth, and possibly on other planets such as Mars, would have required the presence of liquid water and a continuous supply of prebiotic organic compounds. The delivery of organic matter by asteroids, comets, and carbonaceous meteorites could have contributed to the early Earth's prebiotic inventory by seeding the planet with biologically important organic compounds. A wide variety of prebiotic organic compounds have previously been detected in the Murchison CM type carbonaceous chondrite including amino acids, purines and pyrimidines'. These compounds play a major role in terrestrial biochemistry and are integral components of proteins, DNA and RNA. In this study we developed a new extraction technique using sublimation in order to isolate purines and pyrimidines from Murchison2, which is cleaner and more time efficient that traditional methods3. Several purines including adenine, guanine, hypoxanthine and xanthine were positively identified by high performance liquid chromatography and ultraviolet absorption detection in our Murchison extracts. The purines detected in Murchison do not correlate with the distribution of nucleobases found in geological environments on Earth4. Moreover, the abundance of extraterrestrial amino acids and the low level of terrestrial amino acid contaminants found in Murchison', support the idea that the purines in t h s meteorite are extraterrestrial in origin.

Glavin, D. P.↗
NASA NTRS1974

GC-MS in the analysis of organic compounds in meteorites

The application of an analytical approach combining gas chromatography with mass spectrometry (GC-MS) has shown that the amino acid composition of meteorite extracts is quite complex. A computer was used in the evaluation of the data obtained in the investigations. The computer programs developed have been concerned solely with the mass spectra of amino acids. Specialized programs have been written to determine the number of carbon atoms in an amino acid which is a member of any of three subclasses.

Lawless, J. G.↗
DOE OSTI2022

Ultra-fast microwave regeneration of CO 2 solid sorbents for energy-efficient direct air capture

Large-scale deployment of direct air capture (DAC) technologies has become critical for mitigating climate change. Towards this end, energy-efficient regeneration of the sorbents used in the process of carbon capture from air is very important to significantly reduce the high operational cost of DAC. Guanidine compounds can be used with environmentally friendly aqueous amino acids (e.g., potassium sarcosinate) for fast and effective CO 2 capture from air, and have a strong potential for low-energy CO 2 release and sorbent regeneration. In this process, the amino acid absorbs the CO 2 from the air, and the guanidine compounds react with the CO 2 -rich amino acid solution and crystallize as an insoluble carbonate salt. Separation and thermal regeneration of the precipitated guanidine carbonate salt leads to an overall low-temperature and low-energy direct air capture process. Effective CO 2 release from the solid guanidine compound can be achieved by mild heating at 120 °C. Here, in this study, to overcome the relatively inefficient traditional conductive heating of the crystalline solid (i.e., Methylglyoxal-bis(iminoguanidine) carbonate, MGBIG carbonate), we evaluated the feasibility of microwave heating of MGBIG carbonate in terms of power requirement, radiation time, and solids mass for efficient CO 2 desorption. The energy consumption needed by a microwave oven and a conventional oven to regenerate the same mass of the sorbent was directly measured to compare the total energy required per unit mass of regenerated sample and provide an understanding of the potential benefits of microwave regeneration. We found that microwave heating effectively regenerates MGBIG carbonate, which may be facilitated by the water molecules that are co-crystallized with carbonate in the guanidine crystals. Microwave heating at 2.54 GHz with 1250 W is up to 17 times faster than conventional conductive heating at 160 °C, resulting in 40 % electrical energy reduction. These results indicate that microwave regeneration may be an energy-efficient method for fast regeneration of solid sorbents used for direct air capture.

42 ENGINEERING↗
NASA NTRS1983

Experimental studies related to the origin of the genetic code and the process of protein synthesis - A review

A survey is presented of the literature on the experimental evidence for the genetic code assignments and the chemical reactions involved in the process of protein synthesis. In view of the enormous number of theoretical models that have been advanced to explain the origin of the genetic code, attention is confined to experimental studies. Since genetic coding has significance only within the context of protein synthesis, it is believed that the problem of the origin of the code must be dealt with in terms of the origin of the process of protein synthesis. It is contended that the answers must lie in the nature of the molecules, amino acids and nucleotides, the affinities they might have for one another, and the effect that those affinities must have on the chemical reactions that are related to primitive protein synthesis. The survey establishes that for the bulk of amino acids, there is a direct and significant correlation between the hydrophobicity rank of the amino acids and the hydrophobicity rank of their anticodonic dinucleotides.

Lacey, J. C., Jr.↗
DOE OSTI2023

Atomistic simulations of the Escherichia coli ribosome provide selection criteria for translationally active substrates

As genetic code expansion advances beyond l-α-amino acids to backbone modifications and new polymerization chemistries, delineating what substrates the ribosome can accommodate remains a challenge. The Escherichia coli ribosome tolerates non-l-α-amino acids in vitro, but few structural insights that explain how are available, and the boundary conditions for efficient bond formation are so far unknown. Here we determine a high-resolution cryogenic electron microscopy structure of the E. coli ribosome containing α-amino acid monomers and use metadynamics simulations to define energy surface minima and understand incorporation efficiencies. Reactive monomers across diverse structural classes favour a conformational space where the aminoacyl-tRNA nucleophile is <4 Å from the peptidyl-tRNA carbonyl with a Bürgi–Dunitz angle of 76–115°. Monomers with free energy minima that fall outside this conformational space do not react efficiently. This insight should accelerate the in vivo and in vitro ribosomal synthesis of sequence-defined, non-peptide heterooligomers.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1977

Chemical Evolution and the Origin of Life: Bibliography 1975

This bibliography is the sixth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci.We would like to draw attention to a recently published cumulative bibliography on this same subject: Biochemical Origin of Life: Chemistry and Life. Soil and Water and Its Relationship to Origin of Life. MR - Studies of Prebiotic Polypeptides. Energy, Matter, and Life. Prospects for the Future Orientation of Scientific Research. Photochemical Formation of Self Sustaining Coacervates. Photochemical Formation of Self-Sustaining Coacervates. Comparative Study of Abiogenesis of Cysteine and Other Amino Acids Catalyzed by Various Metal Ions. Protein Structure and the Molecular Evolution of Biological Energy Conversion. Origin of Life. Clues from Relations Between Chemical Compositions of Living Organisms and Natural Environments. Shock Synthesis of Amino Acids II.', Origins of Life 6(1-2). Dynamics of the Chemical Evolution of Earth's Primitive Atmosphere. The Mechanisms of Amino Acids Synthesis by High Temperature Shock-Waves. Theory of Chemical Evolution. Physical Foundations of Probability of Biogenesis.

West, Martha W.↗
DOE OSTI2025

Abundant ammonia and nitrogen-rich soluble organic matter in samples from asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all five nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH 3 -rich fluids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2025

Abundant Ammonia and Nitrogen-Rich Soluble Organic Matter in Samples From Asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identifcation, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all fve nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH3-rich fuids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

Daniel P Glavin↗
NASA NTRS2014

Chirality of Meteoritic Free and IOM-Derived Monocarboxylic Acids and Implications for Prebiotic Organic Synthesis

The origin of homochirality and its role in the development of life on Earth are among the most intriguing questions in science. It has been suggested that carbonaceous chondrites seeded primitive Earth with the initial organic compounds necessary for the origin of life. One of the strongest pieces of evidence supporting this theory is that certain amino acids in carbonaceous chondrites display a significant L-enantiomeric excess (ee), similar to those use by terrestrial life. Analyses of ee in meteoritic molecules other than amino acids would shed more light on the origins of homochirality. In this study we investigated the stereochemistry of two groups of compounds: (1) free monocarboxylic acids (MCAs) from CM2 meteorites LON 94101 and Murchison; and (2) the aliphatic side chains present in the insoluble organic matter (IOM) and extracted in the form of monocarboxylic acids (MCAs) from EET 87770 (CR2) and Orgueil (CI1). Contrary to the well-known ee observed for amino acids in meteorites, we found that meteoritic branched free and IOM-derived MCAs with 5-8 carbon atoms are essentially racemic. The racemic nature of these compounds is used to discuss the possible influence of ultraviolet circularly polarized light (UVCPL) and aqueous alterations on the parent body on chirality observed in in carbonaceous chondrites. 2014 Elsevier Ltd. All rights reserved.

monocarboxylic acids↗
NASA NTRS2010

Cometary Glycine Detected in Stardust-Returned Samples

In January 2006, NASA's Stardust spacecraft returned samples from comet 81P/Wild 2 to Earth. The Stardust cometary collector consisted of aerogel cells lined with aluminum foils designed to capture impacting particles and facilitate removal of the aerogel. Preliminary examinations of these comet-exposed materials revealed a suite of organic compounds, including several amines and amino acids which were later examined in more detail. Methylamine (NH2CH3) and ethylamine (NH2C2H5) were detected in the exposed aerogel at concentrations greatly exceeding those found in control samples, while the amino acid glycine (NH2CH2COOH) was detected in several foil samples as well as in the comet-exposed aerogel. None of these three compounds had been previously detected in comets, although methylamine had been observed in the interstellar medium. Although comparison with control samples suggested that the detected glycine was cometary. the previous work was not able to conclusively identify its origin. Here, we present the results of compound-specific carbon isotopic analysis of glycine in Stardust cometary collector foils. Several foils from the interstellar side of the Stardust collector were also analyzed for amino acid abundance, but concentrations were too low to perform isotopic ana!ysis.

Elsila, Jamie E.↗
NASA NTRS2016

Aliphatic Amines in Antarctic CR2, CM2, and CM1/2 Carbonaceous Chondrites

Meteoritic water-soluble organic compounds provide a unique record of the processes that occurred during the formation of the solar system and the chemistry preceding the origins of life on Earth. We have investigated the molecular distribution, compound-specific delta13C isotopic ratios and enantiomeric compositions of aliphatic monoamines present in the hot acid-water extracts of the carbonaceous chondrites LAP 02342 (CR2), GRA 95229 (CR2), LON 94101 (CM2), LEW 90500 (CM2), and ALH 83100 (CM1/2). Analyses of the concentration of monoamines in these meteorites revealed: (a) the CR2 chondrites studied here contain higher concentrations of monoamines relative to the analyzed CM2 chondrites; (b) the concentration of monoamines decreases with increasing carbon number; and (c) isopropylamine is the most abundant monoamine in these CR2 chondrites, while methylamine is the most abundant amine species in these CM2 and CM1/2 chondrites. The delta13C values of monoamines in CR2 chondrite do not correlate with the number of carbon atoms; however, in CM2 and CM1/2 chondrites, the 13C enrichment decreases with increasing monoamine carbon number. The delta13C values of methylamine in CR2 chondrites ranged from −1 to +10per mille, while in CM2 and CM1/2 chondrites the delta13C values of methylamine ranged from +41 to +59per mille. We also observed racemic compositions of sec-butylamine, 3-methyl-2-butylamine, and sec-pentylamine in the studied carbonaceous chondrites. Additionally, we compared the abundance and delta13C isotopic composition of monoamines to those of their structurally related amino acids. We found that monoamines are less abundant than amino acids in CR2 chondrites, with the opposite being true in CM2 and CM1/2 chondrites. We used these collective data to evaluate different primordial synthetic pathways for monoamines in carbonaceous chondrites and to understand the potential common origins these molecules may share with meteoritic amino acids.

Meteoritic water-soluble organic compounds↗
NASA NTRS2015

Synthetic Biology and the Search for Extraterrestrial Life

"Are we alone?" is one of the primary questions of astrobiology, and whose answer defines our significance in the universe. Unfortunately, this quest is hindered by the fact that we have only one confirmed example of life, that of earth. While this is enormously helpful in helping to define the minimum envelope for life, it strains credulity to imagine that life, if it arose multiple times, has not taken other routes. To help fill this gap, our lab has begun using synthetic biology - the design and construction of new biological parts and systems and the redesign of existing ones for useful purposes - as an enabling technology. One theme, the "Hell Cell" project, focuses on creating artificial extremophiles in order to push the limits for Earth life, and to understand how difficult it is for life to evolve into extreme niches. In another project, we are re-evolving biotic functions using only the most thermodynamically stable amino acids in order to understand potential capabilities of an early organism with a limited repertoire of amino acids.

exobiology↗
NASA NTRS2015

Synthetic Astrobiology

'Are we alone?' is one of the primary questions of astrobiology, and whose answer defines our significance in the universe. Unfortunately, this quest is hindered by the fact that we have only one confirmed example of life, that of earth. While this is enormously helpful in helping to define the minimum envelope for life, it strains credulity to imagine that life, if it arose multiple times, has not taken other routes. To help fill this gap, our lab has begun using synthetic biology - the design and construction of new biological parts and systems and the redesign of existing ones for useful purposes - as an enabling technology. One theme, the "Hell Cell" project, focuses on creating artificial extremophiles in order to push the limits for Earth life, and to understand how difficult it is for life to evolve into extreme niches. In another project, we are re-evolving biotic functions using only the most thermodynamically stable amino acids in order to understand potential capabilities of an early organism with a limited repertoire of amino acids.

universe↗
NASA NTRS2017

Synthetic Astrobiology

"Are we alone?" is one of the primary questions of astrobiology, and whose answer defines our significance in the universe. Unfortunately, this quest is hindered by the fact that we have only one confirmed example of life, that of earth. While this is enormously helpful in helping to define the minimum envelope for life, it strains credulity to imagine that life, if it arose multiple times, has not taken other routes. To help fill this gap, our lab has begun using synthetic biology - the design and construction of new biological parts and systems and the redesign of existing ones for useful purposes - as an enabling technology. One theme, the "Hell Cell" project, focuses on creating artificial extremophiles in order to push the limits for Earth life, and to understand how difficult it is for life to evolve into extreme niches. In another project, we are re-evolving biotic functions using only the most thermodynamically stable amino acids in order to understand potential capabilities of an early organism with a limited repertoire of amino acids.

universe↗
NASA NTRS1984

On the stereoselective aminoacylation of RNA

Gabbay and Kleinman (1970) have found that stereospecific complex formation (noncovalent) occurs between nucleic acids and a number of derivatives of amino acids. However, until recently, chiral selection in any nonenzymatic RNA-aminoacylation reaction was unknown. Profy and Usher (1984) reported that aminoacylation of the 'internal' 2-prime-ester occurred with a significant amount of stereoselection. Profy and Usher (1984) have also observed that aminoacylation of the 'internal' 2-prime-hydroxyl groups of polyribonucleotides by the imidazolide of N-3,5-dinitrobenzoylalanine occurs with chiral selection. In order to obtain further information regarding the considered phenomena, a systematic investigation was initiated of the factors which contribute to the observed stereoselectivity of the aminoacylation reaction. In the present paper, the effect of a change in the amino acid from alanine to leucine is considered along with an investigation of the D- and L-alanyl internal' 2-prime esters of the dinucleoside monophosphate of 3-prime,5-prime-ApA.

Usher, D. A.↗
DOE OSTI2023

Short incubation periods of atypical H-type BSE in cattle with EK211 and KK211 prion protein genotypes after intracranial inoculation

In 2006, a case of atypical H-type BSE (H-BSE) was found to be associated with a germline mutation in the PRNP gene that resulted in a lysine substitution for glutamic acid at codon 211 (E211K). The E211K amino acid substitution in cattle is analogous to E200K in humans, which is associated with the development of genetic Creutzfeldt-Jakob disease (CJD). In the present study, we aimed to determine the effect of the EK211 prion protein genotype on incubation time in cattle inoculated with the agent of H-BSE; to characterize the molecular profile of H-BSE in KK211 and EK211 genotype cattle; and to assess the influence of serial passage on BSE strain. Eight cattle, representing three PRNP genotype groups (EE211, EK211, and KK211), were intracranially inoculated with the agent of H-BSE originating from either a case in a cow with the EE211 prion protein genotype or a case in a cow with E211K amino acid substitution. All inoculated animals developed clinical disease; post-mortem samples were collected, and prion disease was confirmed through enzyme immunoassay, anti-PrP Sc immunohistochemistry, and western blot. Western blot molecular analysis revealed distinct patterns in a steer with KK211 H-BSE compared to EK211 and EE211 cattle. Incubation periods were significantly shorter in cattle with the EK211 and KK211 genotypes compared to the EE211 genotype. Inoculum type did not significantly influence the incubation period. This study demonstrates a shorter incubation period for H-BSE in cattle with the K211 genotype in both the homozygous and heterozygous forms.

60 APPLIED LIFE SCIENCES↗