The reactions of nitrogen heterocycles with acrolein: scope and prebiotic significance

It has been suggested that life began with a self-replicating RNA molecule. However, after much research into the prebiotic synthesis of RNA, the difficulties encountered have lead some to hypothesize that RNA was preceded by a simpler molecule, one more easily synthesized prebiotically. Many of the proposed alternative molecules are based on acrolein, since it reacts readily with nucleophiles, such as the nucleobases, via Michael addition and is readily synthesized from formaldehyde and acetaldehyde. Reports regarding the reactions of nucleobases with concentrated acrolein solutions suggest that this is a plausible reaction mechanism, though there are also reports that the "incorrect" isomers are obtained. The scope and kinetics of the reaction of acrolein with various nitrogen heterocycles are reported here. Reactions of pyrimidines often give N(1) adducts as the major products. Reactions of purines often give N(9) adducts in good yield. The reactions are rapid under neutral to slightly alkaline conditions, and proceed at low temperatures and dilutions. The implications of these findings for the origin of life are discussed.     

Adenine synthesis in interstellar space: mechanisms of prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers

The question whether the nucleobases can be synthesized in interstellar space is of fundamental significance in considerations of the origin of life. Adenine is formally the HCN pentamer, and experiments have demonstrated that adenine is formed under certain conditions by HCN pentamerization in gas, liquid, and condensed phases. Most mechanistic proposals invoke the intermediacy of the HCN tetramer AICN (4), and it is thought that adenine synthesis is completed by addition of the 5(th) HCN to 4 to form amidine 5 and subsequent pyrimidine cyclization. In this context, we have been studying the mechanism for prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers with ab initio electronic structure theory. The calculations model gas phase chemistry, and the results primarily inform discussions of adenine synthesis in interstellar space. Purine formation requires tautomerization of 5 to the conjugated amidine 6 (via hydrogen-tunneling, thermally with H(+) -catalysis, or by photolysis) or to keteneimine 7 (by photolysis). It was found that 5-(N'-formamidinyl)-1H-imidazole-4-carbonitrile (6) can serve as a substrate for proton-catalyzed purine formation under photolytic conditions and N-(4-(iminomethylene)-1H-imidazol-5(4H)-ylidene)formamidine (7) can serve as a substrate for uncatalyzed purine formation under photolytic conditions. The absence of any sizeable activation barrier for the cyclization of 7 to the (Z)-imino form of 9H-adenine (Z)-2 is quite remarkable, and it is this feature that allows for the formation of the purine skeleton from 7 without any further activation.     

一种带锥的内绝热层成型工艺改进

某固体火箭发动机燃烧室为锥筒室，内绝热层很薄，包括复合绝热层和橡胶绝热层两层，由于燃烧室几何形状特殊，无法采用现有的内绝热层成型工艺技术，在分析基础上，得出了该内绝热层压制精密控制方法，利用定位和壳体保护装置，将配制的未硫化粘稠态橡胶通过压涂覆在壳体内壁，精确控制内绝热层的厚度和均匀性，该发动机热试车成功表明，这种内绝热层成工艺技术是有效可行的。     

导弹水下热发射出筒过程流动特性

研究了导弹水下热发射出筒过程的流动特性.采用基于多相流Mixture模型的有限体积法求解RANS方程,考虑了流体的可压缩性、粘性、重力作用、气-水掺混效应和能量交换等各项因素,运用自编UDF模块结合动网格技术,对导弹水下发射出筒过程的轴对称流场进行了数值模拟.计算结果揭示了导弹水下热发射出筒过程中发动机喷管、发射筒内和...     

真空热试验中红外笼对伞状天线非稳态加热过程数值仿真

文章针对真空热试验红外加热装置计算机辅助设计中的非稳态过程模拟问题,以一种较为复杂的伞状天线结构为例,以红外笼作为加热装置,对真空热试验环境下的加热过程进行数值仿真研究。采用红外笼的等效加热面模型简化仿真模型,使计算负荷可以达到工程应用的水平,同时满足模拟精度的要求。数值仿真与试验数据对比证明,所采用的计算方法可以为红外笼等红外加热装置的设计提供准确的非稳态加热过程模拟。     

Pyrite-induced hydrogen peroxide formation as a driving force in the evolution of photosynthetic organisms on an early earth

The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.