Hydrodynamic screening of star polymers in shear flow

The mutual effects of the conformations of a star polymer in simple shear flow and the deformation of the solvent flow field are investigated by a hybrid mesoscale simulation technique. We characterize the flow field near the star polymer as a function of its functionality (arm number) f . A strong screening of the imposed flow is found inside the star polymer, which increases with increasing f . To elucidate the importance of hydrodynamic screening, we compare results for hydrodynamic and random solvents. The dependence of the polymer orientation angle on the Weissenberg number shows a power law behavior with super-universal exponent --independent of hydrodynamic and excluded-volume interactions. In contrast, the polymer rotation frequency changes qualitatively when hydrodynamic interactions are switched on.     

Draining and concentration effects in dynamic light scattering from nonentangled polymers in solution

In this work, the theory of dynamic light scattering from nonentangled polymers in solution is developed. Based on our previous results for the joint Rouse and Zimm beadspring model of the dynamics of a single polymer and taking into account the influence of other polymer coils on the hydrodynamics of the solution, the dynamic structure factor (DSF) of a chosen test polymer is calculated. The DSF and its first cumulant essentially depend on polymer draining and the concentration of the coils. The tendency of the screening of hydrodynamic interactions is demonstrated on the concentration dependence of the bead mean-square displacement and the DSF. The dynamic nature of this screening is a natural consequence of the theory. The first cumulant of the DSF is studied as a function of the scattering vector k, the draining of the polymers and their concentration, and compared to the Rouse and Zimm limits and the well-known simple laws for the scattering at small and large k.     

Polymer collapse in the presence of hydrodynamic interactions

We investigate numerically the dynamical behaviour of a polymer chain collapsing in a dilute solution. The rate of collapse is measured with and without the presence of hydrodynamic interactions. We find that hydrodynamic interactions both accelerate polymer collapse and alter the folding pathway.     

Molecular dynamics study of tethered polymers in shear flow

Single macromolecules can now be isolated and characterized experimentally using techniques such as optical tweezers and videomicroscopy. An interesting and important single-molecule problem is that of the dynamics of a polymer chain tethered to a solid surface and subjected to a shear flow. An experimental study of such a system was reported by Doyle et al. (Phys. Rev. Lett. 84, 4769 (2000)), and their results showed a surprising recirculating motion of the DNA chain. We explore this problem using molecular dynamics computer simulations with explicit hydrodynamic interactions. The dynamical properties of a Freely Jointed Chain (FJC) with Finitely Extensible Nonlinear Elastic (FENE) links are examined in similar conditions (i.e., confined between two surfaces and in the presence of a Poiseuille flow). We see the remarkable cyclic polymer motion observed experimentally, and we show that a simple cross-correlation function can be used to measure the corresponding period of motion. We also propose a new empirical equation relating the magnitude of the shear flow to the amount of chain deformation, an equation that appears to apply for both weak and strong flows. Finally, we report on packing effects near the molecularly flat wall, an associated chain-sticking phenomenon, and the impact of the chain hydrodynamic drag on the local fluid flow.     

丙烯酰胺-甲基丙烯酸共聚物结构的NMR研究

用¹H NMR谱，¹³C NMR谱，DEPT谱，gHMQC，gHMBC二维谱和质子弛豫时间等方法研究了在紫外光辐照条件下丙烯酰胺(AM) -甲基丙烯酸(MAA)共聚合反应，讨论了AM-MAA共聚合反应时间与转化率的关系、共聚单体的连接方式、共聚物序列结构以及不同辐照时间下形成的共聚物链运动. 结果表明在紫外光辐照条件下，AM-MAA共聚物链节中同时存在多种连接方式，当反应时间为45 min时，共聚合转化率可达100%. 从自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）测定中得出，在辐照1小时范围内，时间越长聚合物长链分子运动速度越快，但主链的链段运动变化不明显.     

Anomalous diffusion of a polymer chain in an unentangled melt

Contrary to common belief, hydrodynamic interactions in polymer melts are not screened beyond the monomer length and are important in transient regimes. We show that viscoelastic hydrodynamic interactions (VHIs) lead to anomalous dynamics of a tagged chain in an unentangled melt at t相似文献   

Lagrangian Particle Approach to Large Eddy Simulations of Hydrodynamic Turbulence

The flux of energy from large to small scales in hydrodynamic turbulence controls the dissipation of energy at a given scale in the fluid. An accurate parametrization of this flux is a prerequisite in order to devise reliable methods to simulate turbulent flows without resolving all the scales of motion. This problem is discussed in the context of a particle method based on the Smooth Particles Hydrodynamics algorithm. Motivated by the von Karman–Howarth–Kolmogorov exact relation for the energy flux, and by Lagrangian dynamics considerations we postulate an energy transfer term which is quadratic in the velocity and formally time reversal invariant. The numerical simulation of the model however is observed to spontaneously break the time reversal symmetry, demonstrating that the proposed term acts on average as the desired eddy damping.     

Molecular-dynamics simulations with explicit hydrodynamics II: On the collision of polymers with molecular obstacles

We present a study of the dynamics of single polymers colliding with molecular obstacles using Molecular-dynamics simulations. In concert with these simulations we present a generalized polymer-obstacle collision model which is applicable to a number of collision scenarios. The work focusses on three specific problems: i) a polymer driven by an external force colliding with a fixed microscopic post; ii) a polymer driven by a (plug-like) fluid flow colliding with a fixed microscopic post; and iii) a polymer driven by an external force colliding with a free polymer. In all three cases, we present a study of the length-dependent dynamics of the polymers involved. The simulation results are compared with calculations based on our generalized collision model. The generalized model yields analytical results in the first two instances (cases i) and ii)), while in the polymer-polymer collision example (case iii)) we obtain a series solution for the system dynamics. For the case of a polymer-polymer collision we find that a distinct V-shaped state exists as seen in experimental systems, though normally associated with collisions with multiple polymers. We suggest that this V-shaped state occurs due to an effective hydrodynamic counter flow generated by a net translational motion of the two-chain system.     

Transverse migration of a confined polymer driven by an external force

We demonstrate that a polymer confined to a narrow channel migrates towards the center when driven by an external force parallel to the channel walls. This migration results from asymmetric hydrodynamic interactions between polymer segments and the confining walls. A weak pressure-driven flow, applied in the same direction as the external force, enhances the migration. However, when the pressure gradient and the external force act in opposite directions the polymer can migrate towards the boundaries. Nevertheless, for sufficiently strong forces the polymer always migrates towards the center. A dumbbell kinetic theory explains these results qualitatively. A comparison of our results with experimental measurements on DNA suggests that hydrodynamic interactions in polyelectrolytes are only partially screened. We propose new experiments and analysis to investigate the extent of the screening in polyelectrolyte solutions.