A polymer dispersed liquid crystal was studied by dynamic light scattering. In the experiments, where no electric field is applied, the system exhibits additional slow dynamics to the ones observed in bulk nematic liquid crystals. This slow dynamics gradually disappears with an increasing electric field. While the measured time intensity correlation function does not depend on the scattering vector in the system where no field is applied due to the multiple scattering, its dependence on the electric field shows expected size effects. In confined systems, with typical size , there are no eigenmodes of the orientational fluctuations in droplets with the wave vectors less than the minimal wave vector . We observed a quadratic dependence of the inverse relaxation time on the scattering vector down to a certain scattering vector, below which the relaxation time remains constant. The size calculated from this minimal scattering vector is in agreement with the average droplet size obtained from scanning electron microscope photographs and the atomic force microscope images of our sample. The electric field changes the temperature behavior of the inverse relaxation time near the nematic-isotropic phase transition, which increases with the temperature when the electric field is applied, but decreases when the field is absent.
12 May 2009 in The Journal of Physical Chemistry B
GCn and GCnCG, where n = (G2AG4AG2), fold into well-defined, dimeric G-quadruplexes with unprecedented folding topologies in the presence of Na+ ions as revealed by nuclear magnetic resonance spectroscopy. Both G-quadruplexes exhibit unique combination of structural elements among which are two G-quartets, A(GGGG)A hexad and GCGC-quartet. Detailed structural characterization uncovered the crucial role of 5′-GC ends in formation of GCn and GCnCG G-quadruplexes. Folding in the presence of 15NH4+ and K+ ions leads to 3′–3′ stacking of terminal G-quartets of GCn G-quadruplexes, while 3′-GC overhangs in GCnCG prevent dimerization. Results of the present study expand repertoire of possible G-quadruplex structures. This knowledge will be useful in DNA sequence design for nanotechnological applications that may require specific folding topology and multimerization properties.
A possible engineering of materials with diverse bio- and nano-applications relies on robust self-assembly of oligonucleotides. Bottom-up approach utilizing guanine-rich DNA oligonucleotides can lead to formation of G-wires, nanostructures consisting of continuous stacks of G-quartets. However, G-wire structure and self-assembly process remain poorly understood, although they are crucial for optimizing properties needed for specific applications. Herein, we use nuclear magnetic resonance to get insights at molecular level on how chosen short, guanine-rich oligonucleotides self-assemble into G-wires, whereas complementary methods are used for their characterization. Additionally, unravelling mechanistic details enable us to guide G-wire self-assembly in a controlled manner. MD simulations provide insight why loop residues with considerably different properties, i.e., hydrogen-bond affinity, stacking interactions, electronic effects and hydrophobicity extensively increase or decrease G-wire length. Our results provide fundamental understanding of G-wire self-assembly process useful for future design of nanomaterials with specific properties.