Short complementary B-form DNA oligomers, 6 to 20 base pairs in length, are found to exhibit nematic and columnar liquid crystal phases, even though such duplexes lack the shape anisotropy required for liquid crystal ordering. Structural study shows that these phases are produced by the end-to-end adhesion and consequent stacking of the duplex oligomers into polydisperse anisotropic rod-shaped aggregates, which can order into liquid crystals. Upon cooling mixed solutions of short DNA oligomers, in which only a small fraction of the DNA present is complementary, the duplex-forming oligomers phase-separate into liquid crystal droplets, leaving the unpaired single strands in isotropic solution. In a chemical environment where oligomer ligation is possible, such ordering and condensation would provide an autocatalytic link whereby complementarity promotes the extended polymerization of complementary oligomers.
9 September 2013 in Proceedings of the National Academy of Sciences
Significance: At atomic and molecular levels, particles interact via the immutable laws of quantum mechanics, whereas at nanoscopic and microscopic levels, interactions between colloidal particles can be determined by human design. We exploit DNA self-assembly to produce nanoscopic particles with a controlled number of interacting terminations, providing the particles with valence. Experimental investigation of the collective behavior of such colloids shows that reducing the number of interacting sites results in a significant shrinkage of the gas–liquid coexistence region, with critical parameters decreasing as the valence is reduced. We also observe an unconventional dynamic behavior in the proximity of the critical point. Such findings are relevant to answer fundamental physics issues and potentially to determine the stability region of new DNA-based materials.
Light scattering and precision calorimetry show that the nematic ordering of octylcyanobiphenyl (8CB) filling the connected network of pores of a silica aerogel does not occur via the first-order phase transition characteristic of the bulk. Rather, ordering is continuous with an orientational correlation length never increasing beyond the aerogel pore size. The heat-capacity anomly of the second-order nematic–smectic-A phase transition seen in the bulk is absent or greatly broadened in the aerogel.
We present experimental and theoretical studies of the effects of quenched disorder on one-dimensional crystal ordering in three dimensions. This fragile smectic liquid crystal layering, the material with the simplest positional order, is also the most easily deformed periodic structure and is, therefore, profoundly affected by disorder, introduced here by confinement in silica aerogel. Theory and experiment combine to characterize this system to an extraordinary degree, their close accord producing a coherent picture: crystal ordering is lost, giving way to extended short-range correlations that exhibit universal structure and scaling, anomalous layer elasticity, and glassy dynamics.
We describe the use of a bright-field microscope for dynamic light scattering experiments on weakly scattering samples. The method is based on collecting a time sequence of microscope images and analyzing them in the Fourier space to extract the characteristic time constants as a function of the scattering wave vector. We derive a theoretical model for microscope imaging that accounts for (a) the three-dimensional nature of the sample, (b) the arbitrary coherence properties of the light source, and (c) the effect of the finite numerical aperture of the microscope objective. The model is tested successfully against experiments performed on a colloidal dispersion of small spheres in water, by means of the recently introduced differential dynamic microscopy technique [R. Cerbino and V. Trappe, Phys. Rev. Lett. 100, 188102 (2008)]. Finally, we extend our model to the class of microscopy techniques that can be described by a linear space-invariant imaging of the density of the scattering centers, which includes, for example, dynamic fluorescence microscopy.
Innovative technical solutions to realize optical biosensors with improved performance are continuously proposed. Progress in material fabrication enables developing novel substrates with enhanced optical responses. At the same time, the increased spectrum of available biomolecular tools, ranging from highly specific receptors to engineered bioconjugated polymers, facilitates the preparation of sensing surfaces with controlled functionality. What remains often unclear is to which extent this continuous innovation provides effective breakthroughs for specific applications. In this review, we address this challenging question for the class of label‐free optical biosensors, which can provide a direct signal upon molecular binding without using secondary probes. Label‐free biosensors have become a consolidated approach for the characterization and screening of molecular interactions in research laboratories. However, in the last decade, several examples of other applications with high potential impact have been proposed. We review the recent advances in label‐free optical biosensing technology by focusing on the potential competitive advantage provided in selected emerging applications, grouped on the basis of the target type. In particular, direct and real‐time detection allows the development of simpler, compact, and rapid analytical methods for different kinds of targets, from proteins to DNA and viruses. The lack of secondary interactions facilitates the binding of small‐molecule targets and minimizes the perturbation in single‐molecule detection. Moreover, the intrinsic versatility of label‐free sensing makes it an ideal platform to be integrated with biomolecular machinery with innovative functionality, as in case of the molecular tools provided by DNA nanotechnology.