Extended De Gennes Regime Research Articles

Diffusion of knots in nanochannel-confined DNA molecules.

We used Langevin dynamics simulations without hydrodynamic interactions to probe knot diffusion mechanisms and the time scales governing the evolution and the spontaneous untying of trefoil knots in nanochannel-confined DNA molecules in the extended de Gennes regime. The knot untying follows an "opening up process," wherein the initially tight knot continues growing and fluctuating in size as it moves toward the end of the DNA molecule before its annihilation at the chain end. The mean knot size increases significantly and sub-linearly with increasing chain contour length. The knot diffusion in nanochannel-confined DNA molecules is subdiffusive, with the unknotting time scaling with chain contour length with an exponent of 2.64 ± 0.23 to within a 95% confidence interval. The scaling exponent for the mean unknotting time vs chain contour length, along with visual inspection of the knot conformations, suggests that the knot diffusion mechanism is a combination of self-reptation and knot region breathing for the simulated parameters.

Diffusion of Knotted DNA Molecules in Nanochannels in the Extended de Gennes Regime

We study the diffusion of T4 GT7 deoxyribonucleic acid (DNA) molecules confined in nanochannels with an effective size of 307 nm before and after knot formation. The measured DNA chain diffusivity is 0.0243 ± 0.0009 μm²/s for unknotted DNA molecules and 0.014 ± 0.001 μm²/s for the DNA molecules that contain knots with an estimated knot contour length of 9 ± 2 μm. The reduced diffusivity in the presence of large knots indicates that the DNA–wall friction, rather than the shortening of the nondraining molecule, dominates the friction of knotted DNA in the extended de Gennes regime of nanochannel confinement.

Single-Molecule DNA Extension in Rectangular and Square Profile Nanochannels in the Extended de Gennes Regime

Experiments measuring the extension of moderately confined double-stranded DNA within nanochannels have consistently shown a stronger scaling relationship between extension length and nanochannel c...

Evidence for the extended de Gennes regime of a semiflexible polymer in slit confinement.

We use off-lattice, pruned-enriched Rosenbluth method (PERM) simulations to compute the confinement free energy of a real wormlike chain of effective width w and persistence length lp in a slit of height H. For slit heights much larger than the persistence length of the polymer and much smaller than the thermal blob size, the excess free energy of the confined chain is consistent with a modified version of the scaling theory for the extended de Gennes regime in a channel that reflects the blob statistics in slit confinement. Explicitly, for channel sizes [Formula: see text], the difference between the confinement free energy of the real chain and that of an ideal chain scales like w/H.

Comparison of a stripe and slab confinement for ring and linear macromolecules in nanochannel.

The combined effects of the channel asymmetry and the closed chain topology on the chain extension, structure factor, and the orientation correlations were studied using coarse-grained molecular dynamics simulations for moderate chain lengths. These effects are related to applications in linearization experiments with a DNA molecule in nanofluidic devices. According to the aspect ratio, the channels are classified as a stripe or slabs. The chain segments do not have any freedom to move in the direction of the narrowest stripe size, being approximately the same size as the segment size. The chains of both ring and linear topologies are extended more in a stripe than in a slab; this effect is strengthened for a ring. For a ring in a stripe, the extension-confinement strength dependence leads to effective Flory exponents even larger than 3/4, which is characteristic for a self-avoiding two-dimensional chain. While the chain extension-confinement strength dependence for both topologies conforms to the de Gennes regime in a stripe, a linear chain undergoes gradual transition to the pseudoideal regime as the slab height increases in the slab-like confinement. For a confined circle, the onset of the pseudoideal regime is shifted to larger slab heights. The structure factor confirms the absence of the pseudoideal and extended de Gennes regime in a stripe and the transition from the extended to the pseudoideal regime of a circular and linear chain upon increasing the slab heights.

Finite-size corrections for confined polymers in the extended de Gennes regime.

Theoretical results for the extension of a polymer confined to a channel are usually derived in the limit of infinite contour length. But experimental studies and simulations of DNA molecules confined to nanochannels are not necessarily in this asymptotic limit. We calculate the statistics of the span and the end-to-end distance of a semiflexible polymer of finite length in the extended de Gennes regime, exploiting the fact that the problem can be mapped to a one-dimensional weakly self-avoiding random walk. The results thus obtained compare favorably with pruned-enriched Rosenbluth method (PERM) simulations of a three-dimensional discrete wormlike chain model of DNA confined in a nanochannel. We discuss the implications for experimental studies of linear λ-DNA confined to nanochannels at the high ionic strengths used in many experiments.

Kirkwood diffusivity of long semiflexible chains in nanochannel confinement.

We compute the axial diffusivity of asymptotically long semiflexible polymers confined in square channels. Our calculations employ the Kirkwood approximation of the mobility tensor by combining computational fluid dynamics (CFD) calculations of the hydrodynamic tensor in channel confinement with pruned-enriched Rosenbluth method (PERM) simulations of a discrete wormlike chain model. Three key results emerge from our study. First, for the classic de Gennes regime, we confirm that Brochard and de Gennes' blob theory correctly predicts the scaling of the axial diffusivity, contrary to the conclusions of previous analyses. Second, for the extended de Gennes regime, we show that a modified blob theory, which has been used to incorporate the effect of local stiffness on DNA diffusion in nanoslits, explains the deviation from the prediction of classic blob theory for diffusion in nanochannels. Third, we provide a calculation similar to the modified blob theory to explain the relative insensitivity of the diffusivity to channel size for channels between the extended de Gennes regime and the Odijk regime, which is the most relevant regime for experiments and technological applications of DNA confinement in nanochannels. Our results are not only relevant to the dynamics of confined semiflexible polymers such as DNA, but also reveal interesting analogies between confinement in channels and slits.

Nanoconfined Circular and Linear DNA: Equilibrium Conformations and Unfolding Kinetics

Studies of circular DNA confined to nanofluidic channels are relevant both from a fundamental polymer-physics perspective and due to the importance of circular DNA molecules in vivo. We here observe the unfolding of DNA from the circular to linear configuration as a light-induced double strand break occurs, characterize the dynamics, and compare the equilibrium conformational statistics of linear and circular configurations. This is important because it allows us to determine to which extent existing statistical theories describe the extension of confined circular DNA. We find that the ratio of the extensions of confined linear and circular DNA configurations increases as the buffer concentration decreases. The experimental results fall between theoretical predictions for the extended de Gennes regime at weaker confinement and the Odijk regime at stronger confinement. We show that it is possible to directly distinguish between circular and linear DNA molecules by measuring the emission intensity from the DNA. Finally, we determine the rate of unfolding and show that this rate is larger for more confined DNA, possibly reflecting the corresponding larger difference in entropy between the circular and linear configurations.

Confined polymers in the extended de Gennes regime.

We show that the problem of describing the conformations of a semiflexible polymer confined to a channel can be mapped onto an exactly solvable model in the so-called extended de Gennes regime. This regime (where the polymer is neither weakly nor strongly confined) has recently been intensively studied experimentally and by means of computer simulations. The exact solution predicts precisely how the conformational fluctuations depend upon the channel width and upon the microscopic parameters characterizing the physical properties of the polymer.

DNA confined in a two-dimensional strip geometry

Semiflexible polymers characterized by the contour length L and persistent length confined in a spatial region D have been described as a series of “spherical blobs” and “deflecting lines” by de Gennes and Odjik for and , respectively. Recently new intermediate regimes (extended de Gennes and Gauss-de Gennes) have been investigated by Tree et al. (Phys. Rev. Lett., 110 (2013) 208103). In this letter we derive scaling relations to characterize these transitions in terms of universal scaled fluctuations in d-dimension as a function of , and D, and show that the Gauss-de Gennes regime is absent and the extended de Gennes regime is vanishingly small for polymers confined in a 2D strip. We validate our claim by an extensive Brownian dynamics (BD) simulation which also reveals that the prefactor A used to describe the chain extension in the Odjik limit is independent of the physical dimension d and is the same as previously found by Yang et al. (Phys. Rev. E, 76 (2007) 011804). Our studies are relevant for optical maps of DNA stretched inside a nanostrip.

Extended de Gennes Regime of DNA Confined in a Nanochannel

Scaling regimes for polymers confined to tubular channels are well established when the channel cross-sectional dimension is either very small (Odjik regime) or large (classic de Gennes regime) relative to the polymer Kuhn length. However, experiments of confined polymers using DNA as a model system are usually located in the intermediate region between these two regimes. In the literature, controversy exists regarding the existence of the extended de Gennes regime in this intermediate region. Here we use simulations and theory to reconcile conflicting theories and confirm the existence of extended de Gennes regime. We show that prior work did not support the notion of this regime because of the use of a wrong confinement free energy. In a broad sense, the extended de Gennes regime corresponds to the situation when excluded volume interaction is weaker than thermal energy. Such a situation also occurs in many other cases, such as semidilute polymer solutions and polymers under tension. This work should be...

Comparisons of a Polymer in Confinement versus Applied Force

The similarities and differences between geometric and tensile constraints on polymers have not been fully investigated. Here we use theory (blob models) and simulations to present a comprehensive comparison between polymers in these two situations. For a polymer in good solvent, the effect of tensile force f on extension in the Pincus regime is similar to the effect of cylindrical confinement in the de Gennes regime after mapping the characteristic length kBT/f to the cylindrical diameter D, where kBT is the thermal energy. However, the comparison of the effects of tension and confinement on extension is lacking when kBT/f and D are less than the thermal blob size b, referred to as extended Pincus regime and extended de Gennes regime, respectively. In the extended Pincus regime, force can still segregate the ideal-coils with the size of ∼kBT/f, resulting in the scaling of extension L∥ ∼ (kBT/f)−1. In the extended de Gennes regime, excluded volume interaction is not sufficient to segregate the ideal-coils...

A systematic study of DNA conformation in slitlike confinement

DNA conformation in slitlike confinement is studied using Monte Carlo simulation and scaling theory. We focus on analysing the in-plane DNA extension as a function of slit height and DNA properties, such as contour length, persistence length and width. Similar to tube confinement, we identify an extended de Gennes regime which is prevalent in many experimental studies. However, unlike previous studies in tubes, we find two highly confined regimes (so called Odijk regimes) that depend on chain crossing. Our results support the majority of experiments which display a gradual transition into the Odijk regime and give new insight into the importance of chain width for DNA in nanoslits.