Structural and Dynamical Characteristics of Short-Chain Branched Ring Polymer Melts at Interface under Shear Flow.

We present a detailed analysis of the interfacial chain structure and dynamics of confined polymer melt systems under shear over a wide range of flow strengths using atomistic nonequilibrium molecular dynamics simulations, paying particular attention to the rheological influence of the closed-loop ring geometry and short-chain branching. We analyzed the interfacial slip, characteristic molecular mechanisms, and deformed chain conformations in response to the applied flow for linear, ring, short-chain branched (SCB) linear, and SCB ring polyethylene melts. The ring topology generally enlarges the interfacial chain dimension along the neutral direction, enhancing the dynamic friction of interfacial chains moving against the wall in the flow direction. This leads to a relatively smaller degree of slip (ds) for the ring-shaped polymers compared with their linear analogues. Furthermore, short-chain branching generally resulted in more compact and less deformed chain structures via the intrinsically fast random motions of the short branches. The short branches tend to be oriented more perpendicular (i.e., aligned in the neutral direction) than parallel to the backbone, which is mostly aligned in the flow direction, thereby enhancing the dynamic wall friction of the moving interfacial chains toward the flow direction. These features afford a relatively lower ds and less variation in ds in the weak-to-intermediate flow regimes. Accordingly, the interfacial SCB ring system displayed the lowest ds among the studied polymer systems throughout these regimes owing to the synergetic effects of ring geometry and short-chain branching. On the contrary, the structural disturbance exerted by the highly mobile short branches promotes the detachment of interfacial chains from the wall at strong flow fields, which results in steeper increasing behavior of the interfacial slip for the SCB polymers in the strong flow regime compared to the pure linear and ring polymers.

Nonequilibrium Monte Carlo simulations of entangled polymer melts under steady shear flow.

We present a nonequilibrium Monte Carlo (MC) methodology based on expanded nonequilibrium thermodynamic formalism to simulate entangled polymeric materials undergoing steady shear flow. Motivated by the standard kinetic theory for entangled polymers, a second-rank symmetric conformation tensor based on the entanglement segment vector was adopted in the expanded statistical-ensemble based MC method as the nonequilibrium structural variable that properly represents the deformed structure of the system by the flow. The corresponding (second-rank symmetric) conjugate thermodynamic force variable was introduced to simulate an external flow field. As a test case, we applied the GENERIC MC to C400H802 entangled linear polyethylene melts in a wide range of shear rates. Detailed analysis of the GENERIC MC results for various structural and rheological properties (such as chain size, chain orientation, mesoscale chain configuration, topological properties, and material functions) was carried out via direct comparison with the corresponding NEMD results. Overall, the GENERIC MC is shown to predict the general trends of the nonequilibrium properties of polymer systems reasonably for a wide range of flow strengths (i.e., 0.5 ≤ De ≤ 540). In conjunction with NEMD, the present MC method can thus be used to extract fundamental thermodynamic information (nonequilibrium entropy and free energy functions) of entangled polymeric systems under various flow types. Despite the general consistency between the GENERIC MC and NEMD results, some quantitative discrepancies appear in the intermediate-to-strong flow regime. This behavior stems from the inherent mean-field nature of the MC force field which is applied to the individual entanglement segments independently and uniformly along the chain, without accounting for any flow-induced structural or dynamical correlations between segments.

Developmental expression of transferrin binding protein in oligodendrocyte lineage cells of the embryonic chick spinal cord.

Oligodendrocytes develop from precursor cells in the neuroepithelium of the ventral ventricular zone. Oligodendrocytes in the different stages of development are characterized by expression of a number of different marker molecules such as myelin genes, growth factors, and specific antigens. We have previously identified that transferrin binding protein (TfBP), a member of heat shock protein 90 families, is a novel avian ER-associated membrane protein that is specifically localized in oligodendrocytes in adult chicken CNS. In this study we describe the developmental expression of TfBP in the embryonic chick spinal cord. A few, distinct, TfBP+ cells appeared at the lateral margin of the subventricular neuroepithelium of the spinal cord at E7. Thereafter, some TfBP+ cells, exhibited a migrative form of unipolar or bipolar shape occurred around E8 in the mantle layer, midway between the neuroepithelium and the marginal layer of the primitive spinal cord. Thereafter, the TfBP+ cells rapidly increased in number as well as their staining intensity, and overall distribution of TfBP+ cells at E15 was comparable to that of a mature spinal cord. Our observations suggest that TfBP is expressed in the subpopulation of oligodendrocyte lineage in the development and a putative role of TfBP in relation to transferrin and iron trafficking is considered.