Metal-catalyzed degradation and racemization of amino acids in iron sulfate brines under simulated martian surface conditions

Icarus ◽  
2010 ◽  
Vol 207 (1) ◽  
pp. 124-132 ◽  
Author(s):  
Adam P. Johnson ◽  
Lisa M. Pratt
Icarus ◽  
2011 ◽  
Vol 211 (2) ◽  
pp. 1162-1178 ◽  
Author(s):  
A.P. Johnson ◽  
L.M. Pratt ◽  
T. Vishnivetskaya ◽  
S. Pfiffner ◽  
R.A. Bryan ◽  
...  

2002 ◽  
Vol 74 (1) ◽  
pp. 159-166 ◽  
Author(s):  
Iwao Ojima

Recent development in the transition metal-catalyzed cyclization reactions for organic syntheses in the author's laboratories is summarized, which includes (i) novel silylcarbocyclizations (SiCaCs) and carbonylative carbotricyclizations, (ii) intramolecular silylformylations and desymmerization of siloxydiynes by sequential double silylformylation, (iii) efficient total synthesis of (+)-prosopinine, (iv) enantioselective desymmetrization of aminodienes, and (iv) new and efficient routes to 1-azabicyclo[x.y.0]alkane amino acids. All these processes are catalyzed by Rh or Rh­Co complexes, and useful for rapid and efficient construction of a variety of heterocyclic and carbocyclic compounds. Mechanisms of these new carbocyclization and cyclohydrocarbonylation reactions are also discussed.


2008 ◽  
Vol 74 (16) ◽  
pp. 5159-5167 ◽  
Author(s):  
Patricia Fajardo-Cavazos ◽  
Andrew C. Schuerger ◽  
Wayne L. Nicholson

ABSTRACTMost planetary protection research has concentrated on characterizing viable bioloads on spacecraft surfaces, developing techniques for bioload reduction prior to launch, and studying the effects of simulated martian environments on microbial survival. Little research has examined the persistence of biogenic signature molecules on spacecraft materials under simulated martian surface conditions. This study examined how endogenous adenosine-5′-triphosphate (ATP) would persist on aluminum coupons under simulated martian conditions of 7.1 mbar, full-spectrum simulated martian radiation calibrated to 4 W m−2of UV-C (200 to 280 nm), −10°C, and a Mars gas mix of CO2(95.54%), N2(2.7%), Ar (1.6%), O2(0.13%), and H2O (0.03%). Cell or spore viabilities ofAcinetobacter radioresistens, Bacillus pumilus, andB. subtiliswere measured in minutes to hours, while high levels of endogenous ATP were recovered after exposures of up to 21 days. The dominant factor responsible for temporal reductions in viability and loss of ATP was the simulated Mars surface radiation; low pressure, low temperature, and the Mars gas composition exhibited only slight effects. The normal burst of endogenous ATP detected during spore germination inB. pumilusandB. subtiliswas reduced by 1 or 2 orders of magnitude following, respectively, 8- or 30-min exposures to simulated martian conditions. The results support the conclusion that endogenous ATP will persist for time periods that are likely to extend beyond the nominal lengths of most surface missions on Mars, and planetary protection protocols prior to launch may require additional rigor to further reduce the presence and abundance of biosignature molecules on spacecraft surfaces.


2016 ◽  
Vol 9 (6) ◽  
pp. 425-428 ◽  
Author(s):  
M. Massé ◽  
S. J. Conway ◽  
J. Gargani ◽  
M. R. Patel ◽  
K. Pasquon ◽  
...  

PLoS Biology ◽  
2021 ◽  
Vol 19 (12) ◽  
pp. e3001468
Author(s):  
Gabriel Piedrafita ◽  
Sreejith J. Varma ◽  
Cecilia Castro ◽  
Christoph Messner ◽  
Lukasz Szyrwiel ◽  
...  

The structure of the metabolic network is highly conserved, but we know little about its evolutionary origins. Key for explaining the early evolution of metabolism is solving a chicken–egg dilemma, which describes that enzymes are made from the very same molecules they produce. The recent discovery of several nonenzymatic reaction sequences that topologically resemble central metabolism has provided experimental support for a “metabolism first” theory, in which at least part of the extant metabolic network emerged on the basis of nonenzymatic reactions. But how could evolution kick-start on the basis of a metal catalyzed reaction sequence, and how could the structure of nonenzymatic reaction sequences be imprinted on the metabolic network to remain conserved for billions of years? We performed an in vitro screening where we add the simplest components of metabolic enzymes, proteinogenic amino acids, to a nonenzymatic, iron-driven reaction network that resembles glycolysis and the pentose phosphate pathway (PPP). We observe that the presence of the amino acids enhanced several of the nonenzymatic reactions. Particular attention was triggered by a reaction that resembles a rate-limiting step in the oxidative PPP. A prebiotically available, proteinogenic amino acid cysteine accelerated the formation of RNA nucleoside precursor ribose-5-phosphate from 6-phosphogluconate. We report that iron and cysteine interact and have additive effects on the reaction rate so that ribose-5-phosphate forms at high specificity under mild, metabolism typical temperature and environmental conditions. We speculate that accelerating effects of amino acids on rate-limiting nonenzymatic reactions could have facilitated a stepwise enzymatization of nonenzymatic reaction sequences, imprinting their structure on the evolving metabolic network.


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