Nanoparticle penetration into cell membranes is an interesting phenomenon that may have crucial implications on the nanoparticles' biomedical applications. In this paper, a coarse-grained model for gold nanoparticles (AuNPs) is developed (verified against experimental data available) to simulate their interactions with model lipid membranes. Simulations reveal that AuNPs with different signs and densities of surface charges spontaneously adhere to the bilayer surface or penetrate into the bilayer interior. The potential of mean force calculations show that the energy gains upon adhesion or penetration is significant. In the case of penetration, it is found that defective areas are induced across the entire surface of the upper leaflet of the bilayer and a hydrophilic pore that transports water molecules was formed with its surrounding lipids highly disordered. Penetration and its concomitant membrane disruptions can be a possible mechanism of the two observed phenomena in experiments: AuNPs bypass endocytosis during their internalization into cells and cytotoxicity of AuNPs. It is also found that both the level of penetration and membrane disruption increase as the charge density of the AuNP increases, but in different manners. The findings suggest a way of controlling the AuNP-cell interactions by manipulating surface charge densities of AuNPs to achieve designated goals in their biomedical applications, such as striking a balance between their cellular uptake and cytotoxicity in order to achieve optimal delivery efficiency as delivery agents.

A broad class of engineering problems including penetration, impact and large rotations of solid bodies causes severe numerical problems. For these problems, the constitutive equations are history dependent so material points must be followed; this is difficult to implement in an Eulerian scheme. On the other hand, purely Lagrangian methods typically result in severe mesh distortion and the consequence is ill conditioning of the element stiffness matrix leading to mesh lockup or entanglement. Remeshing prevents the lockup and tangling but then interpolation must be performed for hmtory dependent variables, a process which can introduce errors. Proposed here is an extension of the particle-in-cell method in which particles are interpreted to be material points that are followed through the complete loading process. A fixed Eulerian grid provides the means for determining a spatial gradient. Because the grid can also be interpreted as an updated Lagrangian frame, the usual convection term in the acceleration associated with Eulerian formulations does not appear. With the use of maps between material points and the grid, the advantages of both Eulerian and Lagrangian schemes are utilized so that mesh tangling is avoided while material variables are tracked through the complete deformation history. Example solutions in two dimensions are given to illustrate the robustness of the proposed convection algorithm and to show that typical elastic behavior can be reproduced. Also, it is shown that impact with no slip is handled without any special algorithm°f or bodies governed by elasticity and strain hardening plasticity. *The work described in this report was performed for Sandia National Laboratories under Contract No. AC-1801 M ,S]ER i DISTRtP.__,UTION OF THIS DOCUMENT 18 UNLIMITED This page left blank. TABLE OF CONTENTS°S UMMARY vii 1.0 INTRODUCTION 1 2.0 GOVERNING EQUATIONS 3 3.0 MIXED WEAK FORM OF GOVERNING EQUATIONS 5 4.0 THE CONVECTIVE PHASE 9 5.0 GENERATION OF MATERIAL POINTS 1| 6.0 NUMERICAL ALGORITHM 13 7.0 NUMERICAL EXAMPLES 15 7.1 Rotation Test 7.2 Vibrating solid elastic cylinder 7.3 Impact of two elastic bodies 7.4 Bouncing Bar 7.5 Impact of two inelastic bodies 24 7.6 Impact of an elastic disk with a strain-hardening disk 24 8.0 CONCLUSION 9.0 REFERENCES

Nanothermite composites containing metallic fuel and inorganic oxidizer are gaining importance due to their outstanding combustion characteristics. In this paper, the combustion behaviors of copper oxide/aluminum nanothermites are discussed. CuO nanorods were synthesized using the surfactant-templating method, then mixed or self-assembled with Al nanoparticles. This nanoscale mixing resulted in a large interfacial contact area between fuel and oxidizer. As a result, the reaction of the low density nanothermite composite leads to a fast propagating combustion, generating shock waves with Mach numbers up to 3. © 2007 American Institute of Physics. ͓DOI: 10.1063/1.2787972͔ Nanothermite materials are comprised of a physical mixture of inorganic fuel and oxidizer nanoparticles. Nonhomogenous distribution of fuel and oxidizer has been observed in the microstructures. 1 This produces random hot spot density distribution and decreases the propagation speed of the combustion wave front. It is, therefore, important to achieve homogenous mixing of the oxidizer and fuel components for faster reaction kinetics. This can be achieved by selfassembly of fuel around the solid oxidizer. Enhancement in the combustion wave speed has already been reported for composites containing porous oxidizers and fuel nanoparticles, 2,3 and also for electrostatically charged selfassembled composites. 4 Recently, we reported that higher combustion wave speeds were achieved for the composites of ordered porous Fe 2 O 3 oxidizer and Al nanoparticles 5 as compared with the one containing porous oxidizer with no ordering of the pores and Al nanoparticles. We have also reported the composite of CuO nanorods and Al nanoparticles exhibiting a combustion wave speed of 1500Ϯ 100 m / s, which enhances to 2200 m / s for the self-assembled composites. 6-8 Interestingly, these higher combustion wave speeds are comparable to the lower end values of the detonation velocities ͑e.g., 2000 m / s for hydrocarbon/alkylene-air mixtures, 9 1500-2700 m / s for metallic azides and fulminates, 10 and about 3000 m / s for ammonium nitrate fuel oil͒ for explosives. 11 In conventional explosives, the gases produced during the chemical reaction develop turbulence due to a combined effect of high pressure and rapid shearing of molecular layers generating a shock wave. In a process called deflagration-todetonation transition ͑DDT͒, the wave propagates in the reactive medium creating localized high pressure at the hot spots and, after a certain run-up distance, rapid deflagration can transition to full detonation. 9 This distance depends on the dimensions of the shock tube and also the level of confinement. 9 In the case of low density superthermites, as the adiabatic reaction temperatures are several thousand degrees, the reaction products can volatilize rapidly 12 resulting in an increased level of turbulence and high localized pressures. Because of the low density and multiphase nature of reaction materials, the corresponding Chapman-Jouguet ͑CJ͒ pressure can be much lower ...

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Understanding the interactions of gold nanoparticles (AuNPs) with cellular compartments, especially cell membranes, is of fundamental importance in obtaining their control in biomedical applications. An effort is made in this paper to investigate the interactions of 2.2 nm core AuNPs with negative model bilayer membranes by coarse-grained (CG) molecular dynamics (MD) simulation. The CG model of lipid bilayer was taken from Marrink et al. ( J. Phys. Chem. B 2004, 108, 750-760 ), whereas the CG AuNPs model was developed on the basis of both atomistic MD simulations and experimental data. It was found that AuNPs functionalized with cationic ligands penetrated into the negative bilayer membranes and generated significant disruptions on bilayers. The lipids surrounding the nanoparticle were highly disordered and the bulk surface of the bilayer exhibits some defective areas. Most importantly, it is observed that a nanoscale hole can be formed and expanded spontaneously on the peripheral regions of the 20 × 20 nm bilayer. The expansion of the hole is on the time scale of hundreds of nanosceonds. The fully expanded hole had a radius of ∼5.5 nm and could transport water molecules at a rate of up to ∼1100 molecule/ns. However holes could not be formed on a larger bilayer (28 × 28 nm). The factors that can eliminate hole formation on the bilayer also include the decrease of cationic lignads on the AuNP, the reduction of negative lipids in the bilayer, the release of bilayer surface tension, the lowering of temperature, and the addition of a high concentration of salt. The results suggest that a hole can only be formed on living cell membranes under extreme conditions.

Coarse-grained (CG) molecular dynamics (MD) simulations were carried out to investigate the dynamics of 2.2 nm monolayer-protected gold nanoparticles (AuNPs) in solvents. The effects of ligand length, ligand terminal chemistry, solvents, and temperature were examined. It was found that AuNPs with unmodified alkanethiol ligands formed stable aggregates in water in the time scale of hundreds of nanoseconds (eight nanoparticles). In a particular case, the AuNPs aggregated into an infinite, one-dimensional chainlike assembly instead of clusters of aggregates. The aggregates of AuNPs with short ligand tails seemed to have an amorphous shape, whereas long-tailed AuNPs aggregated into a spherical cluster. The properties of ligand terminals had a dominant influence on the aggregation behavior of AuNPs. Increasing the polarity of the ligand terminals weakened the tendency of aggregation of AuNPs in water. For AuNPs imposed with charged terminals, they did not aggregate even with a high concentration of salt. However the aggregation behavior of AuNPs changed dramatically if the properties of solvent were altered. Temperature increase greatly accelerated the process of aggregation. The results suggest that the dynamics of monolayer-protected AuNPs can be controlled by their surface properties as well as the features of solvents.

The relationship between material softening and structural softening is investigated through the use of a model problem in one dimension. If the size of the softening zone is large the structural softening response is stable under displacement-prescribed loading. For a small size, the softening response is unstable and the loading regime is sensitive to imperfections in stiffness. A nonlocal constitutive equation in which the limit stress is a function of strain and strain gradient is introduced to provide an approach for simulating softening with localization. Implications for the numerical modeling of softening phenomena are given.

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