Dynamics of polymers in flowing colloidal suspensions

Using hydrodynamic simulations we examine the behavior of single polymers in a confined colloidal suspension under flow. We study the conformations of both, collapsed and noncollapsed polymers. Our results show that the presence of the colloids has a pronounced effect on the unfolding and refolding cycles of collapsed polymers, but does not have a large effect for noncollapsed polymers. Further inspection of the conformations reveals that the strong flow around the colloids and the direct physical compressions exerted on a globular polymer diffusing in between colloidal shear bands largely facilitate the initiation and unraveling of the globular chains. These results are important for rheological studies of (bio)polymer-(bio)colloid mixtures.     

Single flexible and semiflexible polymers at high shear: Non-monotonic and non-universal stretching response

Using Brownian hydrodynamic simulation techniques, we study single polymers in shear. We investigate the effects of hydrodynamic interactions, excluded volume, chain extensibility, chain length and semiflexibility. The well-known stretching behavior with increasing shear rate [(g)\dot] \dot{{\gamma}} is only observed for low shear [(g)\dot] \dot{{\gamma}} < [(g)\dot]^max \dot{{\gamma}}^{{\max}}_{} , where [(g)\dot]^max \dot{{\gamma}}^{{\max}}_{} is the shear rate at maximum polymer extension. For intermediate shear rates [(g)\dot]^max \dot{{\gamma}}^{{\max}}_{} < [(g)\dot] \dot{{\gamma}} < [(g)\dot]^min \dot{{\gamma}}^{{\min}}_{} the radius of gyration decreases with increasing shear with minimum chain extension at [(g)\dot]^min \dot{{\gamma}}^{{\min}}_{} . For even higher shear [(g)\dot]^min \dot{{\gamma}}^{{\min}}_{} < [(g)\dot] \dot{{\gamma}} the chain exhibits again shear stretching. This non-monotonic stretching behavior is obtained in the presence of excluded-volume and hydrodynamic interactions for sufficiently long and inextensible flexible polymers, while it is completely absent for Gaussian extensible chains. We establish the heuristic scaling laws [(g)\dot]^max \dot{{\gamma}}^{{\max}}_{} ∼ N ^-1.4 and [(g)\dot]^min \dot{{\gamma}}^{{\min}}_{} ∼ N ^0.7 as a function of chain length N , which implies that the regime of shear-induced chain compression widens with increasing chain length. These scaling laws also imply that the chain response at high shear rates is not a universal function of the Weissenberg number Wi = [(g)\dot] \dot{{\gamma}} t \tau anymore, where t \tau is the equilibrium relaxation time. For semiflexible polymers a similar non-monotonic stretching response is obtained. By extrapolating the simulation results to lengths corresponding to experimentally studied DNA molecules, we find that the shear rate [(g)\dot]^max \dot{{\gamma}}^{{\max}}_{} to reach the compression regime is experimentally realizable.     

The secondary structure of RNA under tension

We study the force-induced unfolding of random disordered RNA or single-stranded DNA polymers. The system undergoes a second-order phase transition from a collapsed globular phase at low forces to an extensive necklace phase with a macroscopic end-to-end distance at high forces. At low temperatures, the sequence inhomogeneities modify the critical behaviour. We provide numerical evidence for the universality of the critical exponents which, by extrapolation of the scaling laws to zero force, contain useful information on the ground-state (f = 0) properties. This provides a good method for quantitative studies of scaling exponents characterizing the collapsed globule. In order to get rid of the blurring effect of thermal fluctuations, we restrict ourselves to the ground state at fixed external force. We analyze the statistics of rearrangements, in particular below the critical force, and point out its implications for force-extension experiments on single molecules. Received 18 June 2002 and Received in final form 23 September 2002 RID="a" ID="a"e-mail: muller@ipno.in2p3.fr     

Arrested swelling of highly entangled polymer globules

Upon aging, a collapsed long chain evolves from a crumpled state to a self-entangled globule which can be thought of as a large knot. Swelling of an equilibrium globule in good solvent is a two-step process: (i) fast swelling into an arrested stretched structure with conserved entanglement topology followed by (ii) slow disentanglement. Using computer simulation, we found both mass-mass (m-m) and entanglement-entanglement (e-e) power law correlations inside the swollen globule. The m-m correlations are characterized by a set of two exponents in agreement with a Flory-type argument. The e-e correlations are also characterized by two exponents, both of them larger (by approximately 0.3) than the related m-m exponents. We interpret this difference as evidence of distance-dependent repulsion E=-0.3ln((rho)k(B)T between entanglements sliding along the polymer chain.     

Rheology of steady-state draining foams

We developed the foam drainage rheology technique in order to perform rheological measurements of aqueous foams at a set liquid fraction epsilon and fixed bubble radius R without the usual difficulties associated with fluid drainage and bubble coarsening. The shear stress exhibits a power-law dependence on strain-rate, tau approximately gamma[over]n where n approximately 0.2. The stress exhibits an inverse dependence on liquid content, tau approximately (1+h'epsilon)(-1), where h'=theta(10) exhibits a diminishing logarithmic trend with gamma[over]. We propose a model based upon film shearing as the dominant source of viscous dissipation.     

Wall shear rate distribution for flow in random sphere packings

The wall shear rate distribution P(gamma) is investigated for pressure-driven Stokes flow through random arrangements of spheres at packing fractions 0.1< or =varphi< or =0.64. For dense packings, P(gamma) is monotonic and approximately exponential. As varphi-->0.1, P(gamma) picks up additional structure which corresponds to the flow around isolated spheres, for which an exact result can be obtained. A simple expression for the mean wall shear rate is presented, based on a force-balance argument.     

Measurement of diffusion in the presence of shear flow

We demonstrate here a method whereby molecular diffusion coefficients may be measured in the presence of the deformational flow field of a rheo-NMR cell. The method, which uses a repetitive CPMG train of rf pulses interspersed with magnetic field gradient pulses, allows the anisotropic diffusion spectrum to be directly probed. We focus on the cylindrical Couette cell, for which the radial, tangential, and axial directions correspond to the hydrodynamic velocity gradient, velocity, and vorticity directions. While ideal Couette flow does not perturb the vorticity direction, it does perturb diffusion measurements for the velocity gradient direction, and to a lesser extent, the velocity direction. We show that with closely spaced gradient pulses operating in a flow-compensating mode, there exists a diffusion limit below which one cannot measure, that scales as T(2)gamma(4), where gamma is the shear rate and T the gradient pulse repetition period. For a typical rheo-NMR cell, and for the more challenging velocity gradient direction, diffusion rates above 10(-12) m(2) s(-1) can be accurately measured (to 1% error) at shear rates up to 3s(-1). We demonstrate the use of the method in measuring the diffusion spectrum of a lyotropic lamellar phase under shear.     

Reentrant coil-to-globule-to-coil transition of a single linear homopolymer chain in a water/methanol mixture

Both water and methanol are good solvents for poly( N-isopropylacrylamide) (PNIPAM) at room temperature, but strangely not a mixture of them. Using narrowly distributed linear PNIPAM chains (M(w) = 2.6x10(7) g/mol and M(w)/M(n)<1.1), we have, for the first time, observed a coil-to-globule-to-coil transition of a single PNIPAM chain when methanol was gradually added into water. This novel reentrant transition leads to insight into the complexation between methanol and water. We also found that the chain was crumpled in its globule state and the globule still contained approximately 80% of solvent in its hydrodynamic volume.     

Collapsed and Adsorbed States of a Directed Polymer Chain in Two Dimensions

A phase diagram for a surface-interacting long flexible partially-directed polymer chain in a two-dimensional poor solvent, where the possibility of collapse in the bulk exists, is determined using exact enumeration methods. We used a model of self-attracting self-avoiding walks and evaluated 30 steps in series. An intermediate phase between the desorbed collapsed and adsorbed expanded phases, having the conformation of a surface-attached globule, is found. The four phases, viz ., (i) desorbed expanded (DE), (ii) desorbed collapsed (DC), (iii) adsorbed expanded (AE), (iv) surface-attached globule (SAG), are found to meet at a multicritical point. These features are in agreement with those of an isotropic (or non-directed) polymer chain.     

Tank treading and unbinding of deformable vesicles in shear flow: determination of the lift force

Deformation and tank-treading motion of flaccid vesicles in a linear shear flow close to a wall are quantitatively studied by light microscopy. Velocities of bounded vesicles obey Goldman's law established for rigid spheres. A progressive tilt and a transition of unbinding of vesicles are evidenced upon increasing the shear rate, gamma;. These observations disclose the existence of a viscous lift force, F(l), depending on the viscosity eta of the fluid, the radius R of the vesicle, its distance h from the substrate, and a monotonous decreasing function f(1-v) of the reduced volume v, in the following manner: F(l) = eta(gamma)(R(3)/h)f(1-v). This relation is valid for vesicles both close to and farther from the substrate.     

Irreversible shear-activated aggregation in non-Brownian suspensions

We have studied the effect of shear on the stability of suspensions made of non-Brownian solid particles. We demonstrate the existence of an irreversible transition where the solid particles aggregate at remarkably low volume fractions (phi approximately 0.1). This shear-induced aggregation is dramatic and exhibits a very sudden change in the viscosity, which increases sharply after a shear-dependent induction time. We show that this induction time is related exponentially to the shear rate, reflecting the importance of the hydrodynamic forces in reducing the repulsive energy barrier that prevents the particles from aggregating.     

The Detection of Unfolding Intermediates of Soybean Lipoxygenase-1 during Urea Denaturation by Fluorescence Spectroscopy

The unfolding of soybean lipoxygenase-1 during urea denaturation has been followed by activity assays and fluorescence measurement. The presence of stable intermediates during unfolding for both ferrous and ferric forms of lipoxygenase-1 were observed. In the presence of 6.0 M urea, the unfolding of soybean lipoxygenase-1, as monitored by fluorescence intensity, is a triphasic process, while the inactivation of the enzyme shows a single-phase kinetics. The rate constant of inactivation is consistent with that of the fast conformational change of the enzyme. Based on these, a minimal scheme containing two intermediates was proposed to interpret the unfolding of lipoxygenase-1 induced by urea.     

Nonequilibrium unfolding of polyelectrolyte condensates in electric fields

Using simulations and scaling methods, the effect of an electric field on a collapsed polyelectrolyte globule is investigated, where conduction by counterions and the polyelectrolyte itself is taken into account. At a critical field E(*), a nonequilibrium transition occurs at which the polyelectrolyte unfolds and aligns parallel to the external field. E(*) is determined using scaling results for the polarizability of a polyelectrolyte globule and exhibits a dependence on the chain length N, E(*) approximately N(-1/2), which might be useful for electrophoretic separation of charged biopolymers.     

Conformations of random polyampholytes

We study the size R(g) of random polyampholytes (i.e., polymers with randomly charged monomers) as a function of their length N. All results of our extensive Monte Carlo simulations can be rationalized in terms of the scaling theory we develop for the Kantor-Kardar necklace model, although this theory neglects the quenched disorder in the charge sequence along the chain. We find approximately N1/2. The elongated globule model, the initial predictions of both Higgs and Joanny ( approximately N1/3) and Kantor and Kardar ( approximately N), and previous numerical estimates are ruled out.     

Limits of the hydrodynamic no-slip boundary condition

A controversial point in fluid dynamics is to distinguish the relative importance of surface roughness and fluid-surface intermolecular interactions in determining the boundary condition. Here hydrodynamic forces were compared for flow of Newtonian fluids past surfaces of variable roughness but similar, poorly wetted, surface chemistry. The critical shear stress and shear rate to observe deviations from predictions using the no-slip boundary condition increased nearly exponentially with increasing roughness and diverged at approximately 6 nm rms roughness. We conclude that local intermolecular interactions dominated when the surface was very smooth, but roughness dominated otherwise. This quantifies the limits of both ideas.     

Conformational Transitions in <Emphasis Type="Italic">Ariesaema curvatum</Emphasis> Lectin: Characterization of an Acid Induced Active Molten Globule

Biophysical characterization of a lectin from Ariesaema curvatum (ACL) was carried out using steady state as well as time resolved fluorescence and CD spectroscopy under various denaturing conditions. An intermediate with altered tryptophan microenvironment was detected in the phase diagram, which exibited pronounced secondary structure and hemagglutinating activity in presence of 0.25 M Gdn–HCl. An acid induced molten- globule like structure possessing activity and higher thermostability was detected. Transition to the molten globule state was reversible in nature. The lectin retained hemagglutinating activity even after incubation at 95 °C. Both chemical and thermal unfolding of the lectin were found to consist of multistate processes. Fluorescence quenching of ACL was strong with acrylamide and KI. The single tryptophan was found to be surrounded by high density of the positively charged amino acid residues as shown by a ten fold higher K_sv for KI compared to that for CsCl. The average lifetime of tryptophan fluorescence increased from 1.24 ns in the native state to 1.72 ns in the denatured state.     

A universal criterion for plastic yielding of metallic glasses with a (T/Tg) 2/3 temperature dependence

Room temperature (TR) elastic constants and compressive yield strengths of approximately 30 metallic glasses reveal an average shear limit gammaC=0.0267+/-0.0020, where tauY=gamma CG is the maximum resolved shear stress at yielding, and G the shear modulus. The gammaC values for individual glasses are correlated with t=TR/Tg , and gamma C for a single glass follows the same correlation (vs t=T/Tg). A cooperative shear model, inspired by Frenkel's analysis of the shear strength of solids, is proposed. Using a scaling analysis leads to a universal law tauCT/G=gammaC0-gammaC1(t)2/3 for the flow stress at finite T where gammaC0=(0.036+/-0.002) and gammaC1=(0.016+/-0.002).     

Shear-dependent boundary slip in an aqueous Newtonian liquid

We report direct measurements of hydrodynamic drainage forces, which show clear evidence of boundary slip in a Newtonian liquid. The degree of boundary slip is found to be a function of the liquid viscosity and the shear rate, as characterized by the slip length, and is up to approximately 20 nm. This has implications for confined biological systems, the permeability of microporous media, and for the lubrication of nanomachines, and will be important in the microcontrol of liquid flow. We also show that current theories of slip do not adequately describe the experimental data.     

Dynamics of a tethered polymer in shear flow

The dynamics of a single polymer tethered to a solid surface in a shear flow was observed using fluorescently labeled DNA chains. Dramatic shear enhanced temporal fluctuations in the chain extension were observed. The rate of these fluctuations initially decreased for increasing shear rate gamma; and increased above a critical gamma;. Simulations revealed that these anomalous dynamics arise from a continual recirculating motion of the chain or cyclic dynamics. These dynamics arise from a coupling of the chain velocity in the flow direction to thermally driven fluctuations of the chain in the shear gradient direction.     

Penetration kinetics of a cumulative jet into brittle materials

The experimental results on the penetration of cumulative jets into brittle materials are analyzed to substantiate the assumption that continuous hydrodynamic penetration is violated. The penetration of a cumulative jet into a brittle material has a jumplike character and consists of hydrodynamic penetration, the collapse of the cavity, and secondary penetration into the collapsed material. For a continuous supply of a cumulative jet, this process is repeated at the penetration depth. The necessary conditions of the secondary penetration consist in a high strength of the brittle material and a high fracture rate, which should provide the spallation and collapse of the cavity walls. Jumplike penetration ends when a rarefaction wave passes to the zone of primary penetration.