Molecular Dynamics Study of Charged Dendrimers in Salt-Free Solution: Effect of Counterions

Polyamidoamine (PAMAM) dendrimers, being protonated under physiological conditions, represent a promising class of nonviral, nano-sized vectors for drug and gene delivery. We performed extensive molecular dynamics simulations of a generic model dendrimer in a salt-free solution with dendrimer's terminal beads positively charged. Solvent molecules as well as counterions were explicitly included as interacting beads. We find that the size of the charged dendrimer depends non-monotonically on the strength of electrostatic interactions demonstrating a maximum when the Bjerrum length equals the diameter of a bead. Many other structural and dynamic characteristics of charged dendrimers are also found to follow this pattern. We address such a behavior to the interplay between repulsive interactions of the charged terminal beads and their attractive interactions with oppositely charged counterions. The former favors swelling at small Bjerrum lengths and the latter promotes counterion condensation. Thus, counterions can have a dramatic effect on the structure and dynamics of charged dendrimers and, under certain conditions, cannot be treated implicitly

influence of specific intermolecular interactions on the thermal and dielectric properties of bulk polymers atomistic molecular dynamics simulations of nylon 6

Specific intermolecular interactions, in particular H-bonding, have a strong influence on the structural, thermal and relaxation characteristics of polymers. We report here the results of molecular dynamics simulations of Nylon 6 which provides an excellent example for the investigation of such an influence. To demonstrate the effect of proper accounting for H-bonding on bulk polymer properties, the AMBER99sb force field is used with two different parametrization approaches leading to two different sets of partial atomic charges. The simulations allowed the study of the thermal and dielectric properties in a wide range of temperatures and cooling rates. The feasibility of the use of the three methods for the estimation of the glass transition temperature not only from the temperature dependence of structural characteristics such as density, but also by using the electrostatic energy and dielectric constant is demonstrated. The values of glass transition temperatures obtained at different cooling rates are practically the same for the three methods. By proper accounting for partial charges in the simulations, a reasonable agreement between the results of our simulations and experimental data for the density, thermal expansion coefficient, static dielectric constant and activation energy of γ and β relaxations is obtained demonstrating the validity of the modeling approach reported

A coarse-grained molecular dynamics study of segmental structure and mobility in capped crosslinked copolymer films

We present results from molecular-dynamics simulations of a generic bead-spring model of copolymer chains confined between solid walls and report on the glass-transition temperature and segmental dynamics as a function of film thickness and mesh size (the end-to-end distance of the subchains in the crosslinked polymer networks). Apparently, the glass-transition temperature displayed a steep increase for mesh-size values much smaller than the radius of gyration of the bulk chains, otherwise it remained invariant to mesh-size variations. The rise in the glass-transition temperature with decreasing mesh size and film thickness was accompanied by a monotonic slowing-down of segmental dynamics on all studied length scales. This observation is attributed to the correspondingly decreased width of the bulk density layer that was obtained in films whose thickness was larger than the end-to-end distance of the bulk polymer chains. To test this hypothesis, additional simulations were performed in which the crystalline walls were replaced with amorphous or rough walls. In the amorphous case, the high polymer density close to the walls vanished, but the dynamic response of the film was not affected. The rough walls, on the other hand, only slightly decreased the density close to the walls and led to a minor slowing-down in the dynamics at large length-scales

Non-Gaussian nature of glassy dynamics by cage to cage motion

A model based on a single Brownian particle moving in a periodic effective field is used to understand the non-Gaussian dynamics in glassy systems of cage escape and subsequent recaging, often thought to be caused by a heterogeneous glass structure. The results are compared to molecular-dynamics simulations of systems with varying complexity: quasi-two-dimensional colloidlike particles, atactic polystyrene, and a dendritic glass. The model nicely describes generic features of all three topologically different systems, in particular around the maximum of the non-Gaussian parameter. This maximum is a measure for the average distance between cages

Deforming glassy polystyrene: Influence of pressure, thermal history, and deformation mode on yielding and hardening

The toughness of a polymer glass is determined by the interplay of yielding, strain softening, and strain hardening. Molecular-dynamics simulations of a typical polymer glass, atactic polystyrene, under the influence of active deformation have been carried out to enlighten these processes. It is observed that the dominant interaction for the yield peak is of interchain nature and for the strain hardening of intrachain nature. A connection is made with the microscopic cage-to-cage motion. It is found that the deformation does not lead to complete erasure of the thermal history but that differences persist at large length scales. Also we find that the strain-hardening modulus increases with increasing external pressure. This new observation cannot be explained by current theories such as the one based on the entanglement picture and the inclusion of this effect will lead to an improvement in constitutive modeling

Three-Dimensional Endoscopy-Assisted Excision and Reconstruction for Metastatic Disease of the Dorsal and Lumbar Spine: Early Results

BACKGROUND: The aim of this study was to explore the role of three-dimensional (3D) endoscopy in surgical management of metastatic disease of the dorsal and lumbar spine. METHODS: This is a prospective study on 33 patients (15 men and 18 women, mean age of 61.6 ± 8.9 years) with biopsy-proven metastatic disease of the spine managed by sequential/staged posterior decompression-stabilization, followed by 3D endoscopy-assisted anterior corpectomy and stabilization with a mesh cage. All patients had significant extradural compression or spinal instability or both. Sixteen patients had neurological deficits. Visual analog scale (VAS), Frenkel grade (neurological deficits), Karnofsky performance status scale, and the 36-item short-form health survey (SF-36) were used for assessment preoperatively and at 3, 6, and 12 months from surgery. RESULTS: At a mean follow-up of 1.7 ± 0.7 years from surgery, 18 patients were alive. VAS showed significant improvement at the latest follow-up compared to preoperative levels (4.39 vs. 6.61, p = 0.001). Karnofsky status did not show any significant improvement. Frenkel grade improved in 5 patients, deteriorated in 4 patients, and remained unchanged in 24 patients. Regarding SF-36 parameters, general health showed deterioration, but role functioning—physical, role functioning—emotional, social functioning, and body pain showed statistically significant improvement. There was no change in physical health, viability, and mental health. Subjectively the surgeons felt better depth perception and smoother surgical experience with the 3D optics technology. The only complication was delayed wound healing in three patients who had a previous history of radiotherapy to the surgical site. CONCLUSIONS: 3D endoscopy is a valuable tool in the management of metastatic spinal disease requiring excision and reconstruction using the combined posterior and anterior approaches. These early results warrant confirmation with more data and longer follow-ups