Molecular dynamics simulations on chitosan/graphene nanocomposites as anticancer drug delivery using systems

Several chitosan (CS) drug delivery systems (DDSs) were designed by molecular dynamics (MD) simulations. The systems were composed of pure graphene (G), P-doped (GP) or N-doped (GN) graphene nanosheets for the anticancer drug cyclophosphamide (CP) with the aim of discovering the most appropriate drug carrier. Furthermore, the temperature influence was investigated on the systems characteristics through performing the simulations at four different temperatures including 25, 35, 45 and 55 °C. The diffusion coefficients and mean square displacements (MSDs) were boosted with the temperature increase. At 55 °C, the CS-G-CP exhibited the greatest diffusion coefficient (0.0658 × 10^–5 cm²/s) but the CS-GN-CP had the smallest diffusion coefficient of 0.0553 × 10^–5 cm²/s and the CS-GP-CP illustrated a medium amount (0.0595 × 10^–5 cm²/s) indicating the most controlled/sustained drug diffusion could occur in the CS-GN-CP which could allow the most efficient drug delivery. Moreover, to evaluate the effects of PEG chains and VC molecule on the drug delivery capacity of the CS-GN-CP cell, they were added to the this system and the CS-GN-CP-PEG2-VC was nominated as the best DDS working at 35 °C (close to the human body temperature) due to it had a relatively high drug loading capacity as well as suitable CP diffusion coefficient and FV, FFV values.     

Study of nanoscratching of polymers by using molecular dynamics simulations

Molecular dynamic simulations are performed to study the nanoscratching behavior of polymers.The effects of scratching depth,scratching velocity and indenter/polymer interaction strength are investigated.It is found that polymer material in the scratching zone around the indenter can be removed in a ductile manner as the local temperature in the scratching zone exceeds glass transition temperature Tg.The recovery of polymer can be more significant when the temperature approaches or exceeds Tg.The tangential force,normal force and friction coefficient increase as the scratching depth increases.A larger scratching velocity leads to more material deformation and higher pile-up.The tangential force and normal force are larger for a larger scratching velocity whereas the friction coefficient is almost independent of the scratching velocities studied.It is also found that stronger indenter/polymer interaction strength results in a larger tangential force and friction coefficient.     

Oxide/polymer nanocomposites as new luminescent materials

It is demonstrated that nanocomposites, consisting of an electrically insulating oxide core and PMMA coating exhibit strong luminescence. This luminescence is connected to the interface, where PMMA is bond via a carboxylate bonding to the surface. In this case, luminescence is originated at the carbonyl group of the coating polymer. With decreasing particle size, this emission shows a blue shift, following a law inversely the ones found for quantum confinement systems. For semi-conducting oxides, such as ZnO, this interface related emission is found additionally to quantum confinement phenomena.     

Slow dynamics of embedded fluid in mesoscopic confining systems as probed by NMR relaxometry

Mesoscopic media such as porous materials or colloidal dispersions strongly influence the dynamics of the embedded fluid. In the strong-adsorption regime, it was recently proposed that the effective surface diffusion on flat surface is anomalous and exhibits long-time pathology, enlarging the time domain of the embedded-fluid dynamics towards the low-frequency regime. An interesting way to probe such a slow interfacial process is to use the field-cycling NMR relaxometry. This technique is used here to probe the fluid dynamics in two types of interfacial systems: i) a colloidal glass made of thin and flat particles; ii) a fully saturated porous media, the Vycor glass. Experimental results are critically compared to either a simple theoretical model of NMR dispersion involving elementary steps of the fluid dynamics near an interface (loops, trains, tails) or Brownian-dynamics simulations performed inside 3D reconstructions of these confined systems.Received: 1 January 2003, Published online: 14 October 2003PACS: 76.60.Es Relaxation effects - 61.43.Gt Powders, porous materials - 82.70.Dd Colloids     

Chain dynamics in a hexadecane melt as seen by neutron scattering and identified by molecular dynamics simulations

Different local and global chain dynamics in a C(16)H(34) melt could be revealed by resolution resolved time-of-flight quasielastic neutron scattering and complementary molecular dynamics simulations. Thereby it has been demonstrated that the measured intermediate scattering functions can validate the simulated data on the pico- to nanosecond timescale. Remarkably the shape of the experimentally measured intermediate scattering functions can be reproduced excellently by molecular dynamics simulations. It was found that although the extracted apparent activation energy corresponds to the long-range diffusion value, the molecular dynamics in this time range are mainly due to local bond rotations and the rotation of entire molecules.     

Molecular dynamics simulations of end-grafted centipede-like polymers with stiff charged side chains

We use molecular dynamics simulations to investigate centipede-like polymers with stiff charged side chains, end-grafted to a planar wall. The effect of the grafting density and the Bjerrum length on the conformational behaviour of the brush is examined in detail. In addition, we make a comparison of centipede-like polyelectrolyte (CPE) brushes with neutral centipede-like polymer (NCP) and linear polyelectrolyte (LPE) brushes. At weak electrostatic interaction, the main chains of the CPE chains adopt a strongly stretched conformation, and the monomer density profiles of side chains exhibit a clear oscillatory behaviour. With increasing Bjerrum length, the CPE brush undergoes a collapse transition. Compared to the CPE brushes, the counterion condensation effect is stronger for the LPE brushes, regardless of whether the electrostatic interaction is weak or strong and of whether the grafting density is low or high. Additionally, it is shown that the architecture of the grafted chains makes a weak contribution to the counterion condensation at strong electrostatic interaction. We also find that the electrostatic repulsion between charged side chains can enhance the stiffness of the main chains and thus limit the range of movement of the free-end monomers.     

Chain conformation in thin polymer layers as revealed by simulations of ideal random walks

A confinement-induced mode was discovered in thin cis-1,4-polyisoprene (PI) layers if the film thickness becomes comparable with the size of the PI coil (A. Serghei, F. Kremer, to be published in Phys. Rev. Lett.). It was assigned to the fluctuation of the terminal subchains which are formed by the immobilization of chain segments at the contact with a confining interface. In the present paper we discuss the results of simulations done in order to gain an additional insight into the nature of this novel relaxation process. It turns out that the simulations of the chains as pinned random walks reproduce most of the essential features observed in the experiment.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 61.20.Ja Computer simulation of liquid structure     

Ultrafast core-hole-induced dynamics in water probed by x-ray emission spectroscopy

The isotope effect and excitation-energy dependence have been measured in the oxygen K-edge x-ray emission spectrum (XES). The use of XES to monitor core decay processes provides information about molecular dynamics (MD) on an ultrafast time scale through the O1s lifetime of a few femtoseconds. Different nuclear masses give rise to differences in the dynamics and the observed isotope effect in XES is direct evidence of the importance of such processes. MD simulations show that even the excitation-energy dependence in the XES is mainly related to differences in core-excited-state dynamics.     

Photoluminescence decay dynamics of silver/porous-silicon nanocomposites formed by metal-assisted etching

We investigate the photoluminescence (PL) properties of silver/porous-silicon (Ag/PSi) nanocomposites prepared by metal-assisted etching in ${\mathrm{Ag}}_2\mathrm{O}/\mathrm{HF}$ solution, on the basis of steady-state and time-resolved PL spectroscopy measurements. The PL intensity and peak position are strongly dependent on the ${\mathrm{Ag}}_2\mathrm{O}$ concentration. Time-resolved PL measurements reveal that the nonradiative rate decreases with an increase in the ${\mathrm{Ag}}_2\mathrm{O}$ concentration for the Ag/PSi nanocomposites. It is found from x-ray photoelectron spectroscopy measurements that the decrease in the nonradiative rate is caused by the formation of ${\mathrm{SiO}}_2$ layers on the PSi surfaces. Further, the number of light-emitting Si nanocrystals in the nanocomposites, which is estimated from the PL decay rate and PL intensity, increases with the ${\mathrm{Ag}}_2\mathrm{O}$ concentration. From the wavelength dependence of the PL decay rate, it is found that the nonradiative rate is considerably dispersive, i.e., the shorter the wavelength, the higher the nonradiative rate.     

Allelomimesis as escape strategy of pedestrians in two-exit confinements

We study the efficacy of allelomimesis as an escape strategy of mobile agents (pedestrians) that aim to leave a two-exit room within the shortest possible time. Allelomimesis is the act of copying one’s kindred neighbors. To escape, an agent employs one of the following strategies: (1) It chooses its own route independently (non-copying, α=0), (2) It imitates the actions of its neighbors at all times (blind copying, α=1), or (3) It either copies or acts independently according to a certain probability that is set by the copying parameter . Not more than one agent could occupy a given room location. An agent’s knowledge of the two exit locations is set by its information content . When left alone, an agent with complete knowledge of the exit whereabouts (β=1) always takes the shortest possible path to an exit. We obtain plots of the (group) evacuation time T and exit throughput Q as functions of α and β for cases where the two exits are near (on same room side) and far (on opposite sides of room) from each other. For an isolated agent, T is inversely proportional to β. The chances of escape for an isolated agent with β≤0.2 are higher with adjacent exits. However, for an agent with β>0.4 the chance is better with opposite exits. In a highly occupied room (occupancy rate R=80%) with adjacent exits, agents with β>0.8 escape more quickly if they employ a mixed strategy of copying and non-copying (0.4<α<0.6). On the other hand, blind copying (α≈1) gives agents with β<0.1 a better chance of escaping from the same room. For the same α and R values, opposite exits allow faster evacuation for agents with β<0.1 due to the likelihood of streaming and the lower probability of exit clogging. Streaming indicates an efficient utilization of an exit and it happens when the arcs that are formed are smaller and arch interference is less likely. Allelomimesis provides a simple yet versatile mechanism for studying the egress behavior of confined crowds in a multi-exit room.     

Bonding and dynamics of surface systems probed by soft X-rays

We review some aspects of the investigation of surface systems with soft X-rays. Examples are presented, showing how core level spectroscopies provide detailed information on the structure, bonding and chemistry of adsorbates and thin layers on surfaces. Core level spectroscopies employed at high brilliance synchrotron light sources allow furthermore access to electron dynamics in the attosecond domain, as we demonstrate for the core hole clock method.     

Bubble dynamics relaxation in aqueous foam probed by multispeckle diffusing-wave spectroscopy

We study the bubble rearrangement dynamics in aqueous foam during the passage from liquidlike to solidlike behavior which follows a transient shear deformation that perturbs the bubble packing. The local dynamics is probed using multispeckle diffusing-wave spectroscopy. We show that following the perturbation the average time between rearrangements relaxes exponentially, with time elapsed since the end of the perturbation. The observed scaling of the characteristic relaxation time with perturbation amplitude and foam age is explained by a schematic coarse-grained model based on the scaling state hypothesis.     

Spinodal decomposition of polymer solutions: molecular dynamics simulations of the two-dimensional case

As a generic model system for phase separation in polymer solutions, a coarse-grained model for hexadecane/carbon dioxide mixtures has been studied in two-dimensional geometry. Both the phase diagram in equilibrium (obtained from a finite size scaling analysis of Monte Carlo data) and the kinetics of state changes caused by pressure jumps (studied by large scale molecular dynamics simulations) are presented. The results are compared to previous work where the same model was studied in three-dimensional geometry and under confinement in slit geometry. For deep quenches the characteristic length scale ?(t) of the formed domains grows with time t according to a power law close to [Formula: see text]. Since in this problem both the polymer density ρ(p) and the solvent density ρ(s) matter, the time evolution of the density distribution P(L)(ρ(p),ρ(s),t) in L × L subboxes of the system is also analyzed. It is found that in the first stage of phase separation the system separates locally into low density carbon dioxide regions that contain no polymers and regions of high density polymer melt that are supersaturated with this solvent. The further coarsening proceeds via the growth of domains of rather irregular shapes. A brief comparison of our findings with results of other models is given.     

Precursor states for charge carrier generation in conjugated polymers probed by ultrafast spectroscopy

Photocurrent experiments using two femtosecond laser pulses are performed on a photodiode using a ladder-type conjugated polymer as the active layer. With a photon energy of 3.1 eV the first pulse excites singlet excitons. A time-delayed second pulse with a photon energy of 2.49 eV leads to a decrease of the photocurrent by exciton depletion due to stimulated emission. S1 excitons being dissociated during their entire lifetime are identified as the only relevant channel for charge carrier generation. Intrachain polaron pairs are also formed on an ultrafast time scale with a yield of approximately 10%. They can be efficiently dissociated by reexcitation with photons of an energy of 1.9 eV.     

Adsorption and spreading of polymers at plane interfaces; theory and molecular dynamics simulations

Nonequilibrium processes play a key role in the adsorption kinetics of macromolecules. It is expected that the competition between transport of polymer towards an interface and its subsequent spreading has a significant influence on the adsorbed amount. An increase of the transport rate can lead to an increase of the adsorbed amount, especially when the polymer has too little time to spread at the interface. In this study we present both molecular dynamics simulations and analytical calculations to describe some aspects of the adsorption kinetics. From MD simulations on a poly(ethylene oxide) chain in vacuum near a graphite surface, we conclude that the spreading process can, in first approximation, be described by either a simple exponential function or by first-order reaction kinetics. Combining these spreading models with the transport equations for two different geometries (stagnation-point flow and overflowing cylinder) we are able to derive analytical equations for the adsorption kinetics of polymers at solid-liquid and at liquid-fluid interfaces. Received: 18 July 1997 / Received in final form: 27 October 1997 / Accepted: 6 November 1997