RESUMO
Alkaline folates self-associate in aqueous solutions to form columnar lyotropic phases. Such phases are made by quadruplexes, which are supramolecular helicoidal structures formed by a stacked array of folate tetramers. High-pressure synchrotron X-ray diffraction is used to analyze alkaline folate quadruplex stability and energetics. Diffraction data show that both inter-helical lateral and tetramer stacking distances decrease as a function of pressure. Lateral and axial quadruplex compressibilities and force constants have been derived and strong correlation between the strength of tetramer stacking and pressure effects demonstrated. In particular, quadruplex rigidity increases by changing Na+ to K+ and by adding excess KCl, as a consequence of increased stacking interactions and quadruplex elongation.
Assuntos
Ácido Fólico/química , Testes de Dureza , Conformação Molecular , Pressão , Difração de Raios X , Força Compressiva , Dimerização , Elasticidade , Modelos MolecularesRESUMO
Lipophilic guanines (LipoGs) in aprotic solvents undergo different self-assembly processes based on different H-bonded motifs. Cylindrical nanotubes made by π-π stacked guanine tetramers (G-quadruplexes) and flat, tape-like aggregates (G-ribbons) have been observed depending on the presence of alkali metal ions. To obtain information on the structural properties and stability of these LipoG aggregates, Small-Angle X-ray Scattering (SAXS) experiments have been performed in dodecane, both in the presence and in the absence of potassium ions. As a result, the occurrence of the two different metallo-responsive architectures (nanoribbons or columnar nanotubes) was confirmed and we reported here for the first time a systematic study on the dependence of the aggregate properties on composition, temperature and molecular unit structure. Even if dodecane was selected to favour LipoG solubility, a strong tendency to self-organize into ordered lyotropic phases was indeed detected.
Assuntos
Guanina/química , Hidrocarbonetos/química , Metais Alcalinos/química , Solventes/química , Alcanos/química , Materiais Biocompatíveis/química , Ligação de Hidrogênio , Íons , Estrutura Molecular , Nanoestruturas/química , Conformação de Ácido Nucleico , Espalhamento a Baixo Ângulo , Solubilidade , TemperaturaRESUMO
The self-assembly of a lipophilic derivative of (5'S)-5',8-cyclo-2'-deoxyguanosine, a mutagenic product formed by hydroxyl radical attack against DNA, has been investigated. This derivative forms, with high fidelity, a dodecameric complex composed of three stacked G-quartets in the presence of strontium picrate. This is the first example of a fully-anti lipophilic G-quadruplex.