Eutectic phases in ice facilitate nonenzymatic nucleic acid synthesis

Polymeric compounds similar to oligonucleotides are relevant to the origin of life and particularly to the concept of an RNA world. Although short oligomers of RNA can be synthesized nonenzymatically under laboratory conditions by second-order reactions in concentrated solutions, there is no consensus on how these polymers could have been synthesized de novo on the early Earth from dilute solutions of monomers. To address this question in the context of an RNA world, we have explored ice eutectic phases as a reaction medium. When an aqueous solution freezes, the solutes become concentrated in the spaces between the ice crystals. The increased concentration offsets the effect of the lower temperature and accelerates the reaction. Here we show that in the presence of metal ions in dilute solutions, frozen samples of phosphoimidazolide-activated uridine react within days at -18 degrees C to form oligouridylates up to 11 bases long. Product yields typically exceed 90%, and approximately 30% of the oligomers include one or more 3'-5' linkages. These conditions facilitate not only the notoriously difficult oligouridylate synthesis, but also the oligomerization of activated cytidylate, adenylate, and guanylate. To our knowledge, this represents the first report to indicate that ice matrices on the early Earth may have accelerated certain prebiotic polymerization reactions.     

The first cell membranes

Organic compounds are synthesized in the interstellar medium and can be delivered to planetary surfaces such as the early Earth, where they mix with endogenous species. Some of these compounds are amphiphilic, having polar and nonpolar groups on the same molecule. Amphiphilic compounds spontaneously self-assemble into more complex structures such as bimolecular layers, which in turn form closed membranous vesicles. The first forms of cellular life required self-assembled membranes that were likely to have been produced from amphiphilic compounds on the prebiotic Earth. Laboratory simulations show that such vesicles readily encapsulate functional macromolecules, including nucleic acids and polymerases. The goal of future investigations will be to fabricate artificial cells as models of the origin of life.     

On the stabilization of ribose by silicate minerals

The RNA-world theory hypothesizes that early Earth life was based on the RNA molecule. However, the notion that ribose, the sugar in RNA, is unstable still casts a serious doubt over this theory. Recently, it has been found that the silicate-mediated formose reaction facilitates the stabilization of ribose. Using accurate quantum chemical calculations, we determined the relative stability of the silicate complexes of arabinose, lyxose, ribose, and xylose with the intent to determine which would form predominantly from a formose-like reaction. Five stereoisomers were investigated for each complex. The stereoisomers of 2:1 ribose-silicate are the more stable ones, to the extent that the least stable of these is even more stable than the most stable stereoisomer of the other 2:1 sugar-silicate complexes. Thus, thermodynamically, a formose-like reaction in the presence of silicate minerals should preferentially form the silicate complex of ribose over the silicate complex of arabinose, lyxose, and xylose.     

Comparison of the roles of nucleotide synthesis, polymerization, and recombination in the origin of autocatalytic sets of RNAs

Ribozymes that act as polymerases and nucleotide synthases are known experimentally, even though no fully self-replicating system has yet been found. If the RNA World hypothesis is true, ribozymes must have arisen initially from within a random abiotic polymerization system. To investigate the origin of the RNA world, we studied a mathematical model of a chemical reaction system describing RNA polymerization. It is supposed that, in absence of ribozymes, polymerization occurs at a small spontaneous rate, and that in the presence of polymerase ribozymes, polymerization occurs at a faster rate that is proportional to the ribozyme concentration. Chains must be longer than a minimum threshold length in order to have the possibility of acting as ribozymes. The reaction system has two stable states that we term dead and living. The dead state is controlled by the small spontaneous rate and has negligible concentration of ribozymes. The living state has high concentration of ribozymes, and the reaction rates are determined by the ribozymes; thus, the system is autocatalytic. Concentration fluctuations in a finite volume can cause a transition to occur from the dead to the living state, that is, an origin of life occurs within this model. We also consider ribozymes that catalyze nucleotide synthesis. We show that living and dead states arise in the presence of synthase ribozymes in the same way as for polymerases. It has been proposed that recombination reactions are a way of generating long RNA chains in the early stages of life. We show that if the possibility of random reversible recombination reactions is added to our model, this does not lead to an increase in long polymer concentration. Thus, if recombination is fully reversible, there is no autocatalytic state controlled by recombination. Nevertheless, recombination can play an important role in ribozyme synthesis if there is an additional process that keeps the recombination reactions out of equilibrium. We modeled a case studied experimentally in which building block strands of moderate length associate due to RNA secondary structure formation. A recombination reaction then occurs between these strands to form a longer sequence that catalyzes its own formation via the recombination reaction. This system has an autocatalytic state, and it is possible for it to arise within our random polymerization system. If complexes formed by associations of shorter strands can act as catalysts without the requirement that the strands be covalently linked, this would alleviate the need for synthesis of very long strands; hence, it makes the emergence of an autocatalytic system from an abiotic random polymerization system much more likely.     

Sequence analysis of trimer isomers formed by montmorillonite catalysis in the reaction of binary monomer mixtures

Oligonucleotides are structurally similar to short RNA strands. Therefore, their formation via non-enzymatic reactions is highly relevant to Gilbert's RNA world scenario (1986) and the origin of life. In laboratory synthesis of oligonucleotides from monomers, it is necessary to remove the water molecules from the reaction medium to shift the equilibrium in favor of oligonucleotide formation, which would have been impossible for reactions that took place in dilute solutions on the early Earth. Model studies designed to address this problem demonstrate that montmorillonite, a phyllosilicate common on Earth and identified on Mars, efficiently catalyzes phosphodiester-bond formation between activated mononucleotides in dilute solutions and produces RNA-like oligomers. The purpose of this study was to examine the sequences and regiospecificity of trimer isomers formed in the reaction of 5'-phosphorimidazolides of adenosine and uridine. Results demonstrated that regiospecificity and sequence specificity observed in the dimer fractions are conserved in their elongation products. With regard to regiospecificity, 61% of the linkages were found to be RNA-like 3',5'-phosphodiester bonds. With regard to sequence specificity, we found that 88% of the linear trimers were hetero-isomers with 61% A-monomer and 39% U-monomer incorporation. These results lend support to Bernal's hypothesis that minerals may have played a significant role in the chemical processes that led to the origin of life by catalyzing the formation of phosphodiester bonds in RNA-like oligomers.     

Origin of informational polymers and the search for non-terran life: protection of the polymeric state of DNA by phosphate minerals

An in-depth analysis of the effects exerted on the DNA backbone by 25 crystal phosphate minerals is reported. Degradation of DNA oligomers was performed with two different reactions: Hydrolysis following Nucleophilic Degradation (HND), initiated by the nucleophilic addition of formamide on both purine and pyrimidine nucleobases, and Hydrolysis following Nucleophilic Substitution (HNS) carried on by water and starting with the removal of a nondegraded base. A complete panel of effects on the phosphoester bonds, from protection to enhanced instability to absence of interference, is described. These effects differ in the different degradation pathways and in different physical-chemical conditions. The relationship between the hardness of the mineral and its protective ability is discussed. In addition to its interest per se, this study was prompted by the observed catalytic abilities of soluble and mineral phosphates (Saladino et al., 2006c) on the synthetic reactions by formamide. The relevance of these observations in the search for nonterran life is discussed.     

Formation of nucleobases from formamide in the presence of iron oxides: implication in chemical evolution and origin of life

Simple compounds like HCN, which have one C and one N, are proposed as the probable precursors for biomonomers. Formamide, a hydrolysis product of HCN, is known as the precursor of various biologically important compounds, for example, nucleobases (purines and pyrimidines). In this paper, we report our results on the synthesis of nucleobases, adenine, cytosine, purine, 9-(hydroxyacetyl) purine, and 4(3H)-pyrimidinone from formamide, using iron oxide (hematite) and oxide hydroxides (goethite and akaganeite) as a catalyst. Goethite and hematite produced purine in higher yield. The products formed were characterized by high-performance liquid chromatography and electrospray ionization mass spectrometry techniques. Results of our study reveal that iron oxides might have worked as efficient prebiotic catalysts.     

Abiotic nitrogen fixation on terrestrial planets: reduction of NO to ammonia by FeS

Understanding the abiotic fixation of nitrogen and how such fixation can be a supply of prebiotic nitrogen is critical for understanding both the planetary evolution of, and the potential origin of life on, terrestrial planets. As nitrogen is a biochemically essential element, sources of biochemically accessible nitrogen, especially reduced nitrogen, are critical to prebiotic chemistry and the origin of life. Loss of atmospheric nitrogen can result in loss of the ability to sustain liquid water on a planetary surface, which would impact planetary habitability and hydrological processes that shape the surface. It is known that NO can be photochemically converted through a chain of reactions to form nitrate and nitrite, which can be subsequently reduced to ammonia. Here, we show that NO can also be directly reduced, by FeS, to ammonia. In addition to removing nitrogen from the atmosphere, this reaction is particularly important as a source of reduced nitrogen on an early terrestrial planet. By converting NO directly to ammonia in a single step, ammonia is formed with a higher product yield (~50%) than would be possible through the formation of nitrate/nitrite and subsequent conversion to ammonia. In conjunction with the reduction of NO, there is also a catalytic disproportionation at the mineral surface that converts NO to NO? and N?O. The NO? is then converted to ammonia, while the N?O is released back in the gas phase, which provides an abiotic source of nitrous oxide.     

The definition of life: a brief history of an elusive scientific endeavor

In spite of the spectacular developments in our understanding of the molecular basis that underlies biological phenomena, we still lack a generally agreed-upon definition of life, but this is not for want of trying. Life is an empirical concept; and, as suggested by the many unsuccessful efforts to define it, this task is likely to remain, at best, a work in progress. Although phenomenological characterizations of life are feasible, a precise definition of life remains an elusive intellectual endeavor. This is not surprising: as Nietszche once wrote, there are concepts that can be defined, whereas others only have a history. The purpose of this essay is to discuss some of the manifold (and often unsatisfactory) definitions of life that have been attempted from different intellectual and scientific perspectives and reflect, at least in part, the key role that historical frameworks play. Although some efforts have been more fruitful, the lack of an all-embracing, generally agreed-upon definition of life sometimes gives the impression that what is meant by life's origin is defined in somewhat imprecise terms and that several entirely different questions are often confused. The many attempts made to reduce the nature of living systems to a single living compound imply that life can be so well defined that the exact point at which it started can be established with the sudden appearance of the first replicating molecule. On the other hand, if the emergence of life is seen as the stepwise (but not necessarily slow) evolutionary transition between the non-living and the living, then it may be meaningless to draw a strict line between them.     

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.     

Hydrogen cyanide polymerization: a preferred cosmochemical pathway

Current research in cosmochemistry shows that crude organic solids of high molecular weight are readily formed in planetary, interplanetary and interstellar environments. Underlying much of this ubiquitous chemistry is a low energy route leading directly to the synthesis of hydrogen cyanide and its polymers. Evidence from laboratory and extraterrestrial investigations suggests that these polymers plus water yield heteropolypeptides, a truly universal process that accounts not only for the past synthesis of protein ancestors on Earth but also for reactions proceeding elsewhere today within our solar system, on planetary bodies and satellites around other stars and in the dusty molecular clouds of spiral galaxies. The existence of this preferred pathway - hydrogen cyanide polymerization - surely increases greatly the probability that carbon-based life is widespread in the universe.     

Application of the Mars Organic Analyzer to nucleobase and amine biomarker detection

The Mars Organic Analyzer (MOA), a portable microfabricated capillary electrophoresis instrument being developed for planetary exploration, is used to analyze a wide variety of fluorescamine-labeled amine-containing biomarker compounds, including amino acids, mono and diaminoalkanes, amino sugars, nucleobases, and nucleobase degradation products. The nucleobases cytosine and adenine, which contain an exocyclic primary amine, were effectively labeled, separated, and detected at concentrations <500 nM. To test the general applicability of the MOA for biomarker detection, amino acids and mono- and diamines were extracted from bacterial cells using both hydrolysis and sublimation followed by analysis. The extrapolated limit of detection provided by the valine biomarker was approximately 4 x 10(3) cells per sample. Products of an NH(4)CN polymerization that simulate a prebiotic synthesis were also successfully isolated via sublimation and analyzed. Adenine and alanine/serine were detected with no additional sample cleanup at 120 +/- 13 microM and 4.1 +/- 1 microM, respectively, corresponding to a reaction yield of 0.04% and 0.0003%, respectively. This study demonstrates that the MOA provides sensitive detection and analysis of low levels of a wide variety of amine-containing organic compounds from both biological and abiotic sources.     

Search for extraterrestrial life using chiral molecules: mandelate racemase as a test case

We have investigated an enzymatic racemization reaction as a marker for extraterrestrial life, which resulted in a change in optical rotation of a mandelic acid over time, as measured by polarimetry. Mandelate racemase was active in aqueous buffer in a temperature range between 0 degrees C and 70 degrees C and also in concentrated ammonium salt solutions and water-in-oil microemulsions in a temperature range between -30 degrees C and 60-70 degrees C; however, the enzyme was not active in several organic cryosolvents. Thus, we have demonstrated that concentrated ammonium salt solutions and water-in-oil microemulsions, both of which are able to form on extraterrestrial planets and moons in the presence of liquid water, are suitable media for enzyme reactions at subzero temperatures. Kinetic data for the mandelate racemase reaction obtained by polarimetry, while reproducible and internally consistent, differed significantly from several sets of data obtained previously by other methods such as chromatography and hydrogen-deuterium exchange. However, we conclude that reactions yielding a polarimetric signal, such as the racemizations employed in this work, are suitable mechanisms by which to utilize a change in chirality over time as a tool to detect signs of life.     

Desperately seeking life on Mars

Humans appear to be obsessed with the idea of finding life on Mars and have latched on to any evidence—however improbable—that might support its existence. Charting the history of the often deceptive scientific (not to mention literary) findings made about Mars, this viewpoint suggests that our desire to find extraterrestrial life says more about the human need for companionship and communication than about the true past of the planet. Nevertheless, ESA's Mars Express should give us a better understanding of the true likelihood of life ever having existed there after its launch in 2003.     

Did life begin on the beach?

Water is one of the prerequisites of life. Further requirements are the existence of a system of interacting organic molecules capable of capturing and converting the supply of external energy and elaborating the replicating function that is needed for propagation. None of this would be possible without the existence of some means of concentrating, selecting, and then containing these mutually interacting substances in proximity to one another, i.e., a primitive cell. Starting from this hypothesis we propose a model for the development of life on Earth. Our model embodies the following new features: (1) rapid cycles of catalysis and transport of material, (2) desegregation (separation by tidal action and degradation by catalysis) as well as segregation (by chromatography on tidal beaches), (3) cross-catalysis instead of auto-catalysis, as well as (4) compartmentalization, although the latter idea is of course not new. But our "lipid first" model, in contrast to earlier "peptide first" or "RNA first" models, provides for the compartments needed to act as a cradle for the subsequent development of information- rich molecules like peptides and RNA. If anything, the earliest information-rich molecules were probably membrane-spanning peptides/proteins.     

基于点击化学反应的键合剂应用研究

为改善ADN基三唑交联固化体系固体推进剂的粘合剂/固体填料间的界面作用,提高其力学性能,设计合成了基于点击化学反应的键合剂N-炔丙基-2,2'-二羟乙基胺(BA-2)、N-炔丙基-3,3'-二丙腈基胺(BA-7),并采用DSC证明2种键合剂与ADN具有良好的相容性;采用DSC和FT-IR表征了键合剂与以GAP为代表的含能粘合剂的反应性,二者可在60℃进行成环反应;测试并计算了键合剂与ADN的界面特性参数,证明BA-2和BA-7与ADN有较好的吸附作用,有望在ADN基三唑交联固化体系取得应用。     

航天器防护高能带电粒子的新方法

低地球轨道的原子氧化学性能非常活泼,能使金属铜氧化。XRD(X射线衍射)、XPS(X射线光电子谱)分析结果表明:原子氧作用后,铜的表面生成了氧化铜和氧化亚铜,从而使铜的导电性能、光学性能、焊接性能和结构强度下降。铜与原子氧的氧化反应与温度有关,随着反应温度的增加,反应更加容易。地面试验结果表明:生成的氧化铜或氧化亚铜在原子氧撞击作用下,从试样表面脱落,并沉积到其他试样的表面,从而对其他表面产生较为严重的污染。该研究结果可为在轨航天器污染控制提供参考。     

AP/RDX/Al/HTPB推进剂用硼酸酯键合剂的合成与应用研究

针对丁羟四组元推进剂存在的工艺性能与力学性能的问题,设计合成了新型硼酸酯键合剂。选用二乙醇胺、1-溴代正丁烷、丙烯腈、冰乙酸为原料,合成了N,N-二羟乙基正丁胺、N-(2-腈乙基)二乙醇胺、N,N-二羟乙基乙酰胺中间体。对二乙醇胺和丙烯腈反应的产物做了红外和气-质联用分析,证实合成产物为目标化合物。利用所合成的中间体及甲基二乙醇胺与硼酸三正丁酯,合成了4种新型硼酸酯键合剂,采用丁羟四组元推进剂配方装药,验证了它们的使用效果。结果表明,新合成的4种键合剂都能明显改善药浆流动流平性,其中BA-3和BA-4具有很好的键合效果,显著提升了推进剂的力学性能。     

Serpentinization and its implications for life on the early Earth and Mars

Ophiolites, sections of ocean crust tectonically displaced onto land, offer significant potential to support chemolithoautotrophic life through the provision of energy and reducing power during aqueous alteration of their highly reduced mineralogies. There is substantial chemical disequilibrium between the primary olivine and pyroxene mineralogy of these ophiolites and the fluids circulating through them. This disequilibrium represents a potential source of chemical energy that could sustain life. Moreover, E (h)-pH conditions resulting from rock- water interactions in ultrabasic rocks are conducive to important abiotic processes antecedent to the origin of life. Serpentinization--the reaction of olivine- and pyroxene-rich rocks with water--produces magnetite, hydroxide, and serpentine minerals, and liberates molecular hydrogen, a source of energy and electrons that can be readily utilized by a broad array of chemosynthetic organisms. These systems are viewed as important analogs for potential early ecosystems on both Earth and Mars, where highly reducing mineralogy was likely widespread in an undifferentiated crust. Secondary phases precipitated during serpentinization have the capability to preserve organic or mineral biosignatures. We describe the petrology and mineral chemistry of an ophiolite-hosted cold spring in northern California and propose criteria to aid in the identification of serpentinizing terranes on Mars that have the potential to harbor chemosynthetic life.     

A theory of circular organization and negative feedback: defining life in a cybernetic context

All life today incorporates a variety of systems controlled by negative feedback loops and sometimes amplified by positive feedback loops. The first forms of life necessarily also required primitive versions of feedback, yet surprisingly little emphasis has been given to the question of how feedback emerged out of primarily chemical systems. One chemical system has been established that spontaneously develops autocatalytic feedback, the Belousov-Zhabotinsky (BZ) reaction. In this essay, I discuss the BZ reaction as a possible model for similar reactions that could have occurred under prebiotic Earth conditions. The main point is that the metabolism of contemporary life evolved from primitive homeostatic networks regulated by negative feedback. Because life could not exist in their absence, feedback loops should be included in definitions of life.