Feuillie Cécile, Sverjensky Dimitri A, Hazen Robert M
Geophysical Laboratory, Carnegie Institution of Washington , 5251 Broad Branch Road North West, Washington, DC 20015, United States.
Langmuir. 2015;31(1):240-8. doi: 10.1021/la504034k. Epub 2014 Dec 22.
The interactions between nucleic acids and mineral surfaces have been the focus of many studies in environmental sciences, in biomedicine, as well as in origin of life studies for the prebiotic formation of biopolymers. However, few studies have focused on a wide range of environmental conditions and the likely modes of attachment. Here we investigated the adsorption of ribonucleotides onto α-alumina surfaces over a wide range of pH, ionic strength, and ligand-to-solid ratio, by both an experimental and a theoretical approach. The adsorption of ribonucleotides is strongly affected by pH, with a maximum adsorption at pH values around 5. Alumina adsorbs high amounts of nucleotides >2 μmol/m(2). We used the extended triple-layer model (ETLM) to predict the speciation of the surface complexes formed as well as the stoichiometry and equilibrium constants. We propose the formation of two surface species: a monodentate inner-sphere complex, dominant at pH <7, and a bidentate outer-sphere complex, dominant at higher pH. Both complexes would involve interactions between the negatively charged phosphate group and the positively charged surface of alumina. Our results provide a better understanding of how nucleic acids attach to mineral surfaces under varying environmental conditions. Moreover, the predicted configuration of nucleotide surface species, bound via the phosphate group, could have implications for the abiotic formation of nucleic acids in the context of the origin of life.
核酸与矿物表面之间的相互作用一直是环境科学、生物医学以及生命起源研究中许多研究的焦点,这些研究涉及生物聚合物的益生元形成。然而,很少有研究关注广泛的环境条件以及可能的附着模式。在这里,我们通过实验和理论方法研究了核糖核苷酸在广泛的pH值、离子强度和配体与固体比例范围内在α-氧化铝表面的吸附情况。核糖核苷酸的吸附受到pH值的强烈影响,在pH值约为5时吸附量最大。氧化铝吸附大量的核苷酸>2μmol/m²。我们使用扩展三层模型(ETLM)来预测形成的表面络合物的形态以及化学计量和平衡常数。我们提出形成两种表面物种:一种单齿内球络合物,在pH<7时占主导;一种双齿外球络合物,在较高pH时占主导。这两种络合物都将涉及带负电荷的磷酸基团与带正电荷的氧化铝表面之间的相互作用。我们的结果有助于更好地理解在不同环境条件下核酸如何附着在矿物表面。此外,通过磷酸基团结合的核苷酸表面物种的预测构型可能对生命起源背景下核酸的非生物形成有影响。