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NASA NTRS1997

Fullerenes, fulleranes and polycyclic aromatic hydrocarbons in the Allende meteorite

In this paper, we confirm our earlier observations of fullerenes (C60 and C70) in the Allende meteorite (Becker et al., 1994a, 1995). Fullerene C60 was also detected in two separate C-rich (approximately 0.5-1.0%) dark inclusions (Heymann et al., 1987) that were hand picked from the Allende sample. The amounts of C60 detected were approximately 5 and approximately 10 ppb, respectively, which is considerably less than what was detected in the Allende 15/21 sample (approximately 100 ppb; Becker et al., 1994a, 1995). This suggests that fullerenes are heterogeneously distributed in the meteorite. In addition, we present evidence for fulleranes, (C60Hx), detected in separate samples by laser desorption (reflectron) time-of-flight (TOF) mass spectrometry (LDMS). The LDMS spectra for the Allende extracts were remarkably similar to the spectra generated for the synthetic fullerane mixtures. Several fullerane products were synthesized using a Rh catalyst (Becker et al., 1993a) and separated using high-performance liquid chromatography (HPLC). Polycyclic aromatic hydrocarbons (PAHs) were also observed ppm levels) that included benzofluoranthene and corannulene, a cup-shaped molecule that has been proposed as a precursor molecule to the formation of fullerenes in the gas phase (Pope et al., 1993).

NASA Center ARC↗

NASA NTRS1991

Surface activation of air oxidation of hydrazine on kaolinite. 2. Consideration of oxidizing/reducing entities in relationship to other compositional, structural, and energetic factors

The rates (previously reported) for the air oxidation of hydrazine on kaolinite and substituent oxides of kaolinite showed a complex dependence on the relative amounts of several structural oxidizing/reducing entities within the reaction-promoting solids. The rates indicated an important role of the clay but no dominant role of any one of the oxidizing/reducing entities. In this paper we review (a) the reaction-promoting activity of these centers as studied in other systems, (b) various spectroscopic results showing interaction between these entities in clays, and (c) reported spectroscopic studies of the complexation between hydrazine and aluminosilicate surfaces as a whole, in an effort to propose a mechanism for the reaction. Whereas some uncertainties remain, the present synthesis concludes that a mechanism operating through single electron/hole transfers and hydrogen atom transfers by discrete centers is adequate to explain the observed rate behaviors including the observed second order dependence of the oxidation rate on catalyst amount. The effects of these operations on the catalyst can result in no alteration of, or complete or partial electronic relaxation of its contingent of trapped separated charge pairs. The degree to which surface complexation as a whole, intercalation, or luminescent processes may also be associated with the reaction cannot be adequately assessed with the information in hand.

NASA Program Exobiology↗

NASA NTRS1998

Preference for internucleotide linkages as a function of the number of constituents in a mixture

Phosphoimidazolide-activated ribomononucleotides (*pN; see Scheme I) are useful substrates for the nonenzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous solutions of *pN (0.01 M) typically yield only small amounts of dimers and traces of oligomers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the percentage yield of the condensation products increases and the yield of the hydrolysis product correspondingly decreases with *pN concentration (Kanavarioti 1997). Here we report product distributions in reactions with one, two, or three reactive components at the same total nucleotide concentration. *pN used as substrates were the nucleoside 5'-phosphate 2-methylimidazolides, 2-MeImpN, with N = cytidine (C), uridine (U), or guanosine (G). Reactions were conducted as self-condensations, i. e., one nucleotide only, with two components in the three binary U,C, U,G, and C,G mixtures, and with three components in the ternary U,C, G mixture. The products are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3', 5'-linked dimers, cyclic dimers, and a small percentage of longer oligomers. The surprising finding was that, under identical conditions, including the same total monomer concentration, the product distribution differs substantially from one reaction to another, most likely due to changing intermolecular interactions depending on the constituents. Even more unexpected was the observed trend according to which reactions of the U,C,G mixture produce the highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the approximately two-fold increase in the percentage yield of internucleotide-linked dimers is not due to a concentration effect or a catalyst, but to the increased complexity of the system from a single to two and three components. These observations, perhaps, provide an example of how increased complexity in relatively simple chemical systems leads to organization of the material and consequently to chemical evolution. A possible link between prebiotic chemistry and the postulated RNA world is discussed.

NASA Discipline Exobiology↗

NASA NTRS1991

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗

NASA NTRS2009

NASA Tech Briefs, May 2009

Topics covered include: Valve-"Health"-Monitoring System; Microstrip Antenna for Remote Sensing of Soil Moisture and Sea Surface Salinity; Biomedical Wireless Ambulatory Crew Monitor; Wireless Avionics Packet to Support Fault Tolerance for Flight Applications; Aerobot Autonomy Architecture; Submillimeter Confocal Imaging Active Module; Traveling-Wave Maser for 32 GHz; System Synchronizes Recordings from Separated Video Cameras; Piecewise-Planar Parabolic Reflectarray Antenna; Reducing Interference in ATC Voice Communication; EOS MLS Level 1B Data Processing, Version 2.2; Auto-Generated Semantic Processing Services; Geospatial Authentication; Maneuver Automation Software; Event Driven Messaging with Role-Based Subscriptions; Estimating Relative Positions of Outer-Space Structures; Fabricating PFPE Membranes for Capillary Electrophoresis; Linear Actuator Has Long Stroke and High Resolution; Installing a Test Tap on a Metal Battery Case; Fabricating PFPE Membranes for Microfluidic Valves and Pumps; Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes; Catalysts for Efficient Production of Carbon Nanotubes; Amorphous Silk Fibroin Membranes for Separation of CO2; "Zero-Mass" Noninvasive Pressure Transducers; Radial-Electric-Field Piezoelectric Diaphragm Pumps; Ejector-Enhanced, Pulsed, Pressure-Gain Combustor; Suppressing Ghost Diffraction in E-Beam-Written Gratings; Target-Tracking Camera for a Metrology System; Polarimetric Imaging using Two Photoelastic Modulators; Miniature Wide-Angle Lens for Small-Pixel Electronic Camera; Modal Filters for Infrared Interferometry; Mo(3)Sb(7-x)Te(x) for Thermoelectric Power Generation; Two-Dimensional Quantum Model of a Nanotransistor; Scanning Miniature Microscopes without Lenses; Manipulating Neutral Atoms in Chip-Based Magnetic Traps; Expansion Compression Contacts for Thermoelectric Legs; Processing Electromyographic Signals to Recognize Words; Physical Principle for Generation of Randomness; DSN Beowulf Cluster-Based VLBI Correlator; Hybrid NN/SVM Computational System for Optimizing Designs; Criteria for Modeling in LES of Multicomponent Fuel Flow; Computerized Machine for Cutting Space Shuttle Thermal Tiles; Orbiting Depot and Reusable Lander for Lunar Transportation; FPGA-Based Networked Phasemeter for a Heterodyne Interferometer; Aquarius Digital Processing Unit; Three-Dimensional Optical Coherence Tomography; Benchtop Antigen Detection Technique using Nanofiltration and Fluorescent Dyes; Isolation of Precursor Cells from Waste Solid Fat Tissue; Identification of Bacteria and Determination of Biological Indicators; Further Development of Scaffolds for Regeneration of Nerves; Chemically Assisted Photocatalytic Oxidation System; Use of Atomic Oxygen for Increased Water Contact Angles of Various Polymers for Biomedical Applications; Crashworthy Seats Would Afford Superior Protection; Open-Access, Low-Magnetic-Field MRI System for Lung Research; Microfluidic Mixing Technology for a Universal Health Sensor; Microfluidic Extraction of Biomarkers using Water as Solvent; Microwell Arrays for Studying Many Individual Cells; Droplet-Based Production of Liposomes; and Identifying and Inactivating Bacterial Spores

Source record↗

NASA NTRS2018

Current Activities in the Advanced Exploration Systems ISRU Project

Media Filter MOXIE support: completed flow performance tests and initial dust loading tests of the MOXIE HEPA filter in the Mars Flow Loop Designed and fabricated prototype full-scale scroll filter for testing of renewable filter performance Mars Flow Loop upgrades: installed more sensitive instrumentation, improved imaging, and increased run duration capability Electrostatic Precipitator (ESP) Plasma-physics based model predicts particle charge and trajectory Characterizing dust environment from fluidized-bed injection dust environment using laser sheet visualization and Fine Particle Analyzer Sabatier Design Study Defined the Sabatier design space, including reactor type, thermal management, gas recycling/separation Modeled Sabatier systems with one or two reactors with different types of thermal management Adding thermal management schemes and recycling and gas separation to model Catalyst Screening Performing compression testing on new and used catalyst pellets Performing vibration testing on different catalyst pellet types under different load conditions Preparing to test catalysts for performance and degradation

In-Situ Resource Utilization↗

NASA NTRS2003

CO2 capture by means of an enzyme-based reactor

We report a means for efficient and selective extraction of carbon dioxide (CO(2)) at low to medium concentration from mixed gas streams. CO(2) capture was accomplished by use of a novel enzyme-based, facilitated transport contained liquid membrane (EBCLM) reactor. The parametric studies we report explore both structural and operational parameters of this design. The structural parameters include carbonic anhydrase (CA) concentration, buffer concentration and pH, and liquid membrane thickness. The operational parameters are temperature, humidity of the inlet gas stream, and CO(2) concentration in the feed stream. The data show that this system effectively captures CO(2) over the range 400 ppm to at least 100,000 ppm, at or around ambient temperature and pressure. In a single pass across this homogeneous catalyst design, given a feed of 0.1% CO(2), the selectivity of CO(2) versus N(2) is 1,090 : 1 and CO(2) versus O(2) is 790 :1. CO(2) permeance is 4.71 x 10(-8) molm(-2) Pa(-1) sec(-1). The CLM design results in a system that is very stable even in the presence of dry feed and sweep gases.

NASA Discipline Life Support Systems↗

NASA NTRS2003

Catalyzed Combustion of Bipropellants for Micro-Spacecraft Propulsion

This paper addresses the need to understand the physics and chemistry involved in propellant combustion processes in micro-scale combustors for propulsion systems on micro-spacecraft. These spacecraft are planned to have a mass less than 50 kilograms with attitude control estimated to be in the 10 milli-Newton thrust class. These combustors are anticipated to be manufactured using Micro Electrical Mechanical Systems (MEMS) technology and are expected to have diameters approaching the quenching diameter of the propellants. Combustors of this size are expected to benefit significantly from surface catalysis processes. Miniature flame tube apparatus is chosen for this study because microtubes can be easily fabricated from known catalyst materials and their simplicity in geometry can be used in fundamental simulations for validation purposes. Experimentally, we investigated the role of catalytically active surfaces within 0.4 and 0.8 mm internal diameter microtubes, with special emphases on ignition processes in fuel rich gaseous hydrogen and gaseous oxygen. Flame thickness and reaction zone thickness calculations predict that the diameters of our test apparatus are below the quenching diameter of the propellants in sub-atmospheric tests. Temperature and pressure rise in resistively heated platinum and palladium microtubes was used as an indication of exothermic reactions. Specific data on mass flow versus preheat temperature required to achieve ignition are presented. With a plug flow model, the experimental conditions were simulated with detailed gas-phase chemistry, thermodynamic properties, and surface kinetics. Computational results generally support the experimental findings, but suggest an experimental mapping of the exit temperature and composition is needed.

Schneider, Steven J.↗

NASA NTRS1990

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Tryk, D.↗

NASA NTRS2004

Fuel Cell/Reformers Technology Development

NASA Glenn Research Center is interested in developing Solid Oxide Fuel Cell for use in aerospace applications. Solid oxide fuel cell requires hydrogen rich feed stream by converting commercial aviation jet fuel in a fuel processing process. The grantee's primary research activities center on designing and constructing a test facility for evaluating injector concepts to provide optimum feeds to fuel processor; collecting and analyzing literature information on fuel processing and desulfurization technologies; establishing industry and academic contacts in related areas; providing technical support to in-house SOFC-based system studies. Fuel processing is a chemical reaction process that requires efficient delivery of reactants to reactor beds for optimum performance, i.e., high conversion efficiency and maximum hydrogen production, and reliable continuous operation. Feed delivery and vaporization quality can be improved by applying NASA's expertise in combustor injector design. A 10 KWe injector rig has been designed, procured, and constructed to provide a tool to employ laser diagnostic capability to evaluate various injector concepts for fuel processing reactor feed delivery application. This injector rig facility is now undergoing mechanical and system check-out with an anticipated actual operation in July 2004. Multiple injector concepts including impinging jet, venturi mixing, discrete jet, will be tested and evaluated with actual fuel mixture compatible with reforming catalyst requirement. Research activities from September 2002 to the closing of this collaborative agreement have been in the following areas: compiling literature information on jet fuel reforming; conducting autothermal reforming catalyst screening; establishing contacts with other government agencies for collaborative research in jet fuel reforming and desulfurization; providing process design basis for the build-up of injector rig facility and individual injector design.

Source record↗

NASA NTRSDate not supplied

Bosch Process Technology Development for Air Revitalization

Closed-loop Environmental Control and Life Support Systems (ECLSS) aim to fully recover resources needed to keep astronauts alive in space– primarily, this means reclaiming oxygen (O2) to breathe and water (H2O) to drink from metabolic products. In air revitalization, this requires reclaiming the oxygen tied up in metabolic carbon dioxide (CO2). The current state of the art for the International Space Station (ISS) uses a Sabatier reaction in a system that has demonstrated a 50% O2 recovery rate. While there are several ongoing projects to improve the recovery of the Sabatier-based process, there are also projects working on an alternative approach centered around the Bosch process. Unlike the Sabatier, which has theoretical limits on maximum O2 recovery, the Bosch process can theoretically recover all of the O2 trapped in metabolic CO2 with only solid carbon (C) as a byproduct. However, the C generated in the process poses a significant challenge, introducing issues with clogging, contamination, and catalyst degradation that ultimately make the Bosch process unfeasible for flight at the current state of development. This poster overviews the promise and challenges of the Bosch process, prior investigations conducted, and current work towards advancing the TRL of Bosch-based O2 recovery systems and dealing with the (C) buildup. It also discusses potential uses of the carbon itself, which could prove to be a useful product in in-situ resource utilization (ISRU) applications.

Lunar↗

NASA NTRS2010

Air Stripping Designs and Reactive Water Purification Processes for the Lunar Surface

Air stripping designs are considered to reduce the presence of volatile organic compounds in the purified water. Components of the wastewater streams are ranked by Henry's Law Constant and the suitability of air stripping in the purification of wastewater in terms of component removal is evaluated. Distillation processes are modeled in tandem with air stripping to demonstrate the potential effectiveness and utility of these methods in recycling wastewater on the Moon. Scaling factors for distillation and air stripping columns are presented to account for the difference in the lunar gravitation environment. Commercially available distillation and air stripping units which are considered suitable for Exploration Life Support are presented. The advantages to the various designs are summarized with respect to water purity levels, power consumption, and processing rates. An evaluation of reactive distillation and air stripping is presented with regards to the reduction of volatile organic compounds in the contaminated water and air. Among the methods presented, an architecture is presented for the evaluation of the simultaneous oxidation of organics in air and water. These and other designs are presented in light of potential improvements in power consumptions and air and water purities for architectures which include catalytic activity integrated into the water processor. In particular, catalytic oxidation of organics may be useful as a tool to remove contaminants that more traditional distillation and/or air stripping columns may not remove. A review of the current leading edge at the commercial level and at the research frontier in catalytically active materials is presented. Themes and directions from the engineering developments in catalyst design are presented conceptually in light of developments in the nanoscale chemistry of a variety of catalyst materials.

Boul, Peter J.↗

NASA NTRS2017

Evolving Maturation of the Series-Bosch System

Human exploration missions to Mars and other destinations beyond low Earth orbit require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. In order to meet this requirement, NASA has continued the development of a Series-Bosch System, a two stage reactor process that reduces carbon dioxide (CO2) with hydrogen (H2) to produce water and solid carbon. Theoretically, the Bosch process can recover 100% of the oxygen (O2) from CO2 in the form of water, making it an attractive option for long duration missions. The Series Bosch system includes a reverse water gas shift (RWGS) reactor, a carbon formation reactor (CFR), an H2 extraction membrane, and a CO2 extraction membrane. In 2016, the results of integrated testing of the Series Bosch system showed great promise and resulted in design modifications to the CFR to further improve performance. This year, integrated testing was conducted with the modified reactor to evaluate its performance and compare it with the performance of the previous configuration. Additionally, a CFR with the capability to load new catalyst and remove spent catalyst in-situ was built. Flow demonstrations were performed to evaluate both the catalyst loading and removal process and the hardware performance. The results of the integrated testing with the modified CFR as well as the flow demonstrations are discussed in this paper.

Stanley, Christine↗

NASA NTRS2017

Evolving Maturation of the Series-Bosch System

Abney, Morgan B.↗

NASA NTRS2009

Synthesis, Decomposition and Characterization of Fe and Ni Sulfides and Fe and CO Nanoparticles for Aerospace Applications

We describe several related studies where simple iron, nickel, and cobalt complexes were prepared, decomposed, and characterized for aeronautics (Fischer-Tropsch catalysts) and space (high-fidelity lunar regolith simulant additives) applications. We describe the synthesis and decomposition of several new nickel dithiocarbamate complexes. Decomposition resulted in a somewhat complicated product mix with NiS predominating. The thermogravimetric analysis of fifteen tris(diorganodithiocarbamato)iron(III) has been investigated. Each undergoes substantial mass loss upon pyrolysis in a nitrogen atmosphere between 195 and 370 C, with major mass losses occurring between 279 and 324 C. Steric repulsion between organic substituents generally decreased the decomposition temperature. The product of the pyrolysis was not well defined, but usually consistent with being either FeS or Fe2S3 or a combination of these. Iron nanoparticles were grown in a silica matrix with a long-term goal of introducing native iron into a commercial lunar dust simulant in order to more closely simulate actual lunar regolith. This was also one goal of the iron and nickel sulfide studies. Finally, cobalt nanoparticle synthesis is being studied in order to develop alternatives to crude processing of cobalt salts with ceramic supports for Fischer-Tropsch synthesis.

Cowen, Jonathan E.↗

NASA NTRS2002

Solid-State Compressor for Space Station Oxygen Recovery

At present, the life support system on the International Space Station Alpha vents overboard the carbon dioxide (CO2) produced by the crew members. Recovering the oxygen contained in the CO2 has the potential to reduce resupply mass by 2000 pounds per year or more, a significant weight that could be used for experimental payloads and other valuable items. The technologies used to remove CO2 from the air and to recover O2 from CO2 are flight-ready; however, the interface between the devices is a problem for the Space Station system. Ames Research Center has developed a new technology that solves the interface issue, possibly allowing closure of the oxygen loop in a spacecraft for the first time. CO2 produced by the crew is removed in the Carbon Dioxide Removal Assembly (CDRA). This device effectively produces a pure CO2 stream, but at a very low pressure. Elsewhere, the oxygen generation system which makes O2 by electrolyzing water produces a hydrogen stream. In principle the CO2 and H2 can react to form methane and water over a suitable catalyst. Water produced in this methane-formation reactor can be returned to the water electrolyzer, where the O2 can be returned to the cabin; however, the methane-formation reactor requires CO2 at a much higher pressure than that produced by the CDRA. Furthermore, the CO2 and H2 are often not available at the same time, due to power management and scheduling on the space station. In order to get the CO2 to the reactor at the right pressure and at the right time, a device or assembly that functions as a vacuum pump, compressor, and storage tank is required.

Finn, John E.↗

NASA NTRS2016

Mission X: Train Like an Astronaut Challenge

The Mission X: Train Like an Astronaut Challenge was developed in 2011 to encourage proper exercise and nutrition at an early age by teaching young people to live and eat like space explorers. The strong correlation between an unhealthy childhood diet and adolescent fitness, and the onset of chronic diseases as an adult is the catalyst for Mission X. Mission X is dedicated to assisting people on a global scale to live healthier lifestyles and learn about human space exploration. The Mission X: Train Like an Astronaut 2015 (MX15) International Challenge hosted almost 40,000 children on 800 teams, 28 countries affiliated with 12 space agencies. The MX15 website included 17 languages. MX15, the fifth annual international fitness challenges sponsored by the NASA Human Research Program worked with the European Space Agency and other space agencies from around the world. In comparison to MX14, MX15 expanded to include four additional new countries, increased the number of students by approximately 68% and the number of teams by 29%. Chile' and South Korea participated in the new fall Astro Charlie Walk Around the Earth Challenge. Pre-challenge training materials were made more readily available from the website. South Korea completed a prospective assessment of the usability of the MX content for improving health and fitness in 212 preschool children and their families. Mission X is fortunate to have the support of the NASA, ESA and JAXA astronaut corps. In MX15, they participated in the opening and closing events as well as while on-board the International Space Station. Italian Astronaut Samantha Cristoretti participated as the MX15 Astronaut Ambassador for health and fitness providing the opening video and other videos from ISS. United Kingdom Astronaut Tim Peake and US Astronaut Kate Rubins have agreed to be the MX Ambassadors for 2016 and 2017 respectively. The MX15 International Working Group Face-to-Face meeting and Closing Event were held at the Agenzia Spaziale Italiana (ASI) in Rome, Italy. A record number of twenty-eight countries participated. Austria and Norway have offered to host the 2016 and 2017 working group meetings. MX16 planning began with the working group meetings and areas of improvement will include another second early challenge to accommodate countries in the Southern Hemisphere, recommended changes to the MX website, development of a more defined approach to metrics, a change to the format of future MX International Working Group meetings, and proposed new activities to be developed by the MX International Educator Working Group. We look forward to welcoming many new participants in 2016!

Lloyd, Charles W.↗

NASA NTRS1996

Kinetic and mechanistic analysis of nonenzymatic, template-directed oligoribonucleotide ligation

The role of divalent cations in the mechanism of pyrophosphate-activated, template-directed oligoribonucleotide ligation has been investigated. The dependence of the reaction rate on Mg2+ concentration suggests a kinetic scheme in which a Mg2+ ion must bind before ligation can proceed. Mn2+, Ca2+, Sr2+, and Ba2+ can also catalyze the reaction. Although Pb2+ and Zn2+ do not catalyze the reaction in the absence of other divalent ions, they significantly modulate the reaction rate when added in the presence of Mg2+, with Pb2+ stimulating the reaction (up to 65-fold) and Zn2+ inhibiting the reaction. The logarithm of the ligation rate increases linearly, with slope of 0.95, as a function of pH, indicating that the reaction involves a single critical deprotonation step. The ligation rates observed with the different divalent metal ion catalysts (Mn2+ > Mg2+ > Ca2+ > Sr2+ = Ba2+) vary inversely with the pKa values of their bound water molecules. The pH profile and these relative ligation rates suggest a mechanism in which a metal-bound hydroxide ion located near the ligation junction promotes catalysis, most likely by deprotonation of the hydroxl nucleophile. The effects of changing either the leaving group or the attacking hydroxyl, together with the large delta S(++) value for oligonucleotide ligation (about -20 eu), are consistent with an associative transition state.

Non-NASA Center↗