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A Global Scale Scenario for Prebiotic Chemistry: Silica-BasedSelf-Assembled Mineral Structures and Formamide

机译:益生元化学的全球规模方案:基于二氧化硅自组装矿物结构和甲酰胺

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摘要

The pathway from simple abiotically made organic compounds to the molecular bricks of life, as we know it, is unknown. The most efficient geological abiotic route to organic compounds results from the aqueous dissolution of olivine, a reaction known as serpentinization (Sleep, N.H., et al. (2004) Proc. Natl. Acad. Sci. USA 101, 12818–12822). In addition to molecular hydrogen and a reducing environment, serpentinization reactions lead to high-pH alkaline brines that can become easily enriched in silica. Under these chemical conditions, the formation of self-assembled nanocrystalline mineral composites, namely silica/carbonate biomorphs and metal silicate hydrate (MSH) tubular membranes (silica gardens), is unavoidable (Kellermeier, M., et al. In Methods in Enzymology, Research Methods in Biomineralization Science (De Yoreo, J., Ed.) Vol. 532, pp 225–256, Academic Press, Burlington, MA). The osmotically driven membranous structures have remarkable catalytic properties that could be operating in the reducing organic-rich chemical potin which they form. Among one-carbon compounds, formamide (NH2CHO) has been shown to trigger the formation of complex prebioticmolecules under mineral-driven catalytic conditions (Saladino, R.,et al. (2001) Biorganic & Medicinal Chemistry, 9, 1249–1253), proton irradiation (Saladino, R., et al.(2015) Proc. Natl. Acad. Sci. USA, 112, 2746–2755),and laser-induced dielectric breakdown (Ferus, M., et al. (2015) Proc Natl Acad Sci USA, 112, 657–662). Here, we showthat MSH membranes are catalysts for the condensation of NH2CHO, yielding prebiotically relevant compounds, including carboxylicacids, amino acids, and nucleobases. Membranes formed by the reactionof alkaline (pH 12) sodium silicate solutions with MgSO4 and Fe2(SO4)3·9H2O show the highest efficiency, while reactions with CuCl2·2H2O, ZnCl2, FeCl2·4H2O, and MnCl2·4H2O showed lowerreactivities. The collections of compounds forming inside and outsidethe tubular membrane are clearly specific, demonstrating that themineral self-assembled membranes at the same time create space compartmentalizationand selective catalysis of the synthesis of relevant compounds. Ratherthan requiring odd local conditions, the prebiotic organic chemistryscenario for the origin of life appears to be common at a universalscale and, most probably, earlier than ever thought for our planet.
机译:据我们所知,从简单的非生物制造的有机化合物到生命的分子障碍的途径尚不清楚。有机化合物最有效的地质非生物途径是橄榄石的水溶,这种反应被称为蛇纹石化(Sleep,N.H.等人(2004),美国国家科学院学报101,12818–12822)。除了分子氢和还原性环境外,蛇纹石化反应还会导致高pH值的碱性盐水变得容易富含二氧化硅。在这些化学条件下,不可避免地会形成自组装的纳米晶体矿物复合物,即二氧化硅/碳酸盐生物形态和金属硅酸盐水合物(MSH)管状膜(二氧化硅花园)(Kellermeier,M.等,在酶学方法中,生物矿化科学的研究方法(De Yoreo,J。,编辑),第532卷,第225-256页,马萨诸塞州伯灵顿,学术出版社。渗透驱动的膜结构具有显着的催化性能,可以在富含还原剂的化学罐中运行它们形成的形式。在一种碳化合物中,甲酰胺(NH2CHO)已被证明可触发复杂益生元的形成分子在矿物驱动的催化条件下(Saladino,R.,等。 (2001)Biorganic&Medicinal Chemistry,9,1249–1253),质子辐照(Saladino,R.,et al。,2001)。(2015年)Proc。 Natl。学院科学美国,112,2746–2755),以及激光引起的介电击穿(Ferus,M.等人(2015)Proc Natl Acad Sci USA,112,657-662)。在这里,我们展示MSH膜是NH2CHO缩合的催化剂,可产生益生元相关化合物,包括羧酸酸,氨基酸和核碱基。反应形成的膜MgSO4和Fe2(SO4)3·9H2O的碱性(pH 12)硅酸钠溶液效率最高,而与CuCl2·2H2O,ZnCl2,FeCl2·4H2O和MnCl2·4H2O的反应效率较低反应性。内部和外部形成的化合物的集合管状膜很明显是特定的,表明矿物自组装膜同时形成空间分隔以及相关化合物合成的选择性催化。而是比需要奇特的局部条件,益生元有机化学生命起源的场景在世界范围内似乎很普遍规模,而且很可能比我们的星球想像的要早。

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