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Using fluorescence microscopy and single-particle tracking, we have directly observed the dynamics of λ-DNA trapped inside poly(acrylamide-co-acrylate) hydrogels under an externally applied electric field. Congruent with the recent discovery of the nondiffusive topologically frustrated dynamical state (TFDS) that emerges at intermediate confinements between the traditional entropic barrier and reptation regimes, we observe the immobility of λ-DNA in the absence of an electric field. The electrophoretic mobility of the molecule is triggered upon application of an electric field with strength above a threshold value Ec. The existence of the threshold value to elicit mobility is attributed to a large entropic barrier, arising from many entropic traps acting simultaneously on a single molecule. Using the measured Ec which depends on the extent of confinement, we have determined the net entropic barrier of up to 130 kBT, which is responsible for the long-lived metastable TFDS. The net entropic barrier from multiple entropic traps is nonmonotonic with the extent of confinement and tends to vanish at the boundaries of the TFDS with the single-entropic barrier regime at lower confinements and the reptation regime at higher confinements. We present an estimate of the mesh size of the hydrogel that switches off the nondiffusive TFDS and releases chin diffusion in the heavily entangled state. 

The single most intrinsic property of nonrigid polymer chains is their ability to adopt enormous numbers of chain conformations, resulting in huge conformational entropy. When such macromolecules move in media with restrictive spatial constraints, their trajectories are subjected to reductions in their conformational entropy. The corresponding free energy landscapes are interrupted by entropic barriers separating consecutive spatial domains which function as entropic traps where macromolecules can adopt their conformations more favorably. Movement of macromolecules by negotiating a sequence of entropic barriers is a common paradigm for polymer dynamics in restrictive media. However, if a single chain is simultaneously trapped by many entropic traps, it has recently been suggested that the macromolecule does not undergo diffusion and is localized into a topologically frustrated dynamical state, in apparent violation of Einstein’s theorem. Using fluorescently labeled λ-DNA as the guest macromolecule embedded inside a similarly charged hydrogel with more than 95% water content, we present direct evidence for this new state of polymer dynamics at intermediate confinements. Furthermore, using a combination of theory and experiments, we measure the entropic barrier for a single macromolecule as several tens of thermal energy, which is responsible for the extraordinarily long extreme metastability. The combined theory–experiment protocol presented here is a determination of single-molecule entropic barriers in polymer dynamics. Furthermore, this method offers a convenient general procedure to quantify the underlying free energy landscapes behind the ubiquitous phenomenon of movement of single charged macromolecules in crowded environments.