Amino Acid Modified RNA Bases as Building Blocks of an Early Earth RNA-Peptide World

Fossils of extinct species allow us to reconstruct the process of Darwinian evolution that led to the species diversity we see on Earth today. The origin of the first functional molecules able to undergo molecular evolution and thus eventually able to create life, are largely unknown. The most prominent idea in the field posits that biology was preceded by an era of molecular evolution, in which RNA molecules encoded information and catalysed their own replication. This RNA world concept stands against other hypotheses, that argue for example that life may have begun with catalytic peptides and primitive metabolic cycles. The question whether RNA or peptides were first is addressed by the RNA-peptide world concept, which postulates a parallel existence of both molecular species. A plausible experimental model of how such an RNA-peptide world may have looked like, however, is absent. Here we report the synthesis and physicochemical evaluation of amino acid containing adenosine bases, which are closely related to molecules that are found today in the anticodon stem-loop of tRNAs from all three kingdoms of life. We show that these adenosines lose their base pairing properties, which allow them to equip RNA with amino acids independent of the sequence context. As such we may consider them to be living molecular fossils of an extinct molecular RNA-peptide world.     

Prebiotic Nucleoside Synthesis: The Selectivity of Simplicity

Ever since the discovery of nucleic acids 150 years ago,^[1] major achievements have been made in understanding and decrypting the fascinating scientific questions of the genetic code.^[2] However, the most fundamental question about the origin and the evolution of the genetic code remains a mystery. How did nature manage to build up such intriguingly complex molecules able to encode structure and function from simple building blocks? What conditions were required? How could the precursors survive the unhostile environment of early Earth? Over the past decades, promising synthetic concepts were proposed providing clarity in the field of prebiotic nucleic acid research. In this Minireview, we show the current status and various approaches to answer these fascinating questions.     

Remarkable improvement of cyclic stability in Li–O2 batteries using ruthenocene as a redox mediator

Nonaqueous Li–O₂ batteries attract attention for their theoretical specific energy density. However, due to the difficulty of decomposition of Li₂O₂, Li–O₂ batteries have high charge overpotential and poor cycling life. So all kinds of catalysts have been studied on the cathode. Compared to heterogeneous solid catalysts, soluble catalysts achieve faster and more effective transport of electrons by reversible redox pairs. Here, we first report ruthenocene (Ruc) as a mobile redox mediator in a Li–O₂ battery. 0.01 mol/L Ruc in the electrolyte effectively reduces the charging voltage by 610 mV. Additionally, Ruc greatly increases the cycling life by four-fold (up to 83 cycles) with a simple ketjen black (KB) cathode. The results of SEM, XPS and XRD confirm that less discharge product residue accumulated after recharge. To verify the reaction mechanisms of the mediator, free energy profiles of the possible reaction pathways based on DFT are provided.     

Shock Processing of Amino Acids Leading to Complex Structures—Implications to the Origin of Life

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the ‘threads’ observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.     

Template‐Directed Copying of RNA by Non‐enzymatic Ligation

The non‐enzymatic replication of the primordial genetic material is thought to have enabled the evolution of early forms of RNA‐based life. However, the replication of oligonucleotides long enough to encode catalytic functions is problematic due to the low efficiency of template copying with mononucleotides. We show that template‐directed ligation can assemble long RNAs from shorter oligonucleotides, which would be easier to replicate. The rate of ligation can be greatly enhanced by employing a 3′‐amino group at the 3′‐end of each oligonucleotide, in combination with an N‐alkyl imidazole organocatalyst. These modifications enable the copying of RNA templates by the multistep ligation of tetranucleotide building blocks, as well as the assembly of long oligonucleotides using short splint oligonucleotides. We also demonstrate the formation of long oligonucleotides inside model prebiotic vesicles, which suggests a potential route to the assembly of artificial cells capable of evolution.     

Valuation and risk assessment of participating life insurance in the presence of credit risk

In participating life insurance, management decisions regarding the asset composition can substantially impact the value of a policy from the policyholders’ perspective as well as the insurer’s risk situation. Due to the long-term guarantees often embedded in these contracts, life insurers typically invest a considerable portion of their capital in long-term assets such as corporate and government bonds. Besides interest rate risk, the value of these bond investments is thus particularly influenced by credit risk. Thus, the aim of this paper is to examine the impact of market risk associated with the asset composition on fair valuation and risk assessment with focus on credit risk and its interaction with equity risk and interest rate risk. Our analysis emphasizes that the consideration of credit risk associated with bonds has a strong impact on the fair valuation and risk measurement in the context of participating life insurance contracts, even in case of higher grade bond exposures.     

组合发电仪的制作

仪器应用生活中常见的材料,仅仅围绕物理学科知识,通过巧妙设计,组装出一系列发电机。旨在让学生明白各种发电机的工作原理,以及能量之间是如何相互转化的,培养学生节约能源,保护环境利用清洁能源的意识。此外本仪器制作简单,便于学生亲手制作,锻炼动手能力的同时,又可提高学习兴趣。     

大自然为什么选择磷主导生命

磷酸单酯和双酯被漫长的进化过程选择为生命体的核心.磷酸酯功能的多样性需要磷酰基转移酶不断地进化来实现.现今磷酰基转移酶的催化机制已经得到了广泛研究.通过高分辨X射线晶体衍射技术(X-ray)与19FNMR的联用,来研究磷酰基转移酶的金属氟化物过渡态类似物,可以从原子层面上阐述磷酰基转移的机理.该催化机理充分地解释了磷酸酯的一对相互"矛盾"的性质,即磷酸酯结构的极其稳定性与磷酰基在信号传导过程中的灵活可调性.通过对元素周期表中其他元素的含氧酸根及其酯的性质的研究,目前还无法找出一个更加合适的元素来替代磷的这些重要功能,因而这些证据都支持了Todd的说法:"哪里有生命,哪里就一定有磷".     

An energy-based microstructure model to account for fatigue scatter in polycrystals

Scatter observed in the fatigue response of a nickel-based superalloy, U720, is linked to the variability in the microstructure. Our approach is to model the energy of a persistent slip band (PSB) structure and use its stability with respect to dislocation motion as our failure criterion for fatigue crack initiation. The components that contribute to the energy of the PSB are identified, namely, the stress field resulting from the applied external forces, dislocation pile-ups, and work-hardening of the material is calculated at the continuum scale. Further, energies for dislocations creating slip in the matrix/precipitates, interacting with the GBs, and nucleating/agglomerating within the PSB are computed via molecular dynamics simulations. Through this methodology, fatigue life is predicted based on the energy of the PSB, which inherently accounts for the microstructure of the material. The present approach circumvents the introduction of uncertainty principles in material properties. It builds a framework based on mechanics of microstructure, and from this framework, we construct simulated microstructures based on the measured distributions of grain size, orientation, neighbor information, and grain boundary character, which allows us to calculate fatigue scatter using a deterministic approach. The uniqueness of the approach is that it avoids the large number of parameters prevalent in previous fatigue models. The predicted lives are in excellent agreement with the experimental data validating the model capabilities.