Methane and carbon dioxide adsorption on edge-functionalized graphene: a comparative DFT study.

With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO(2) and CH(4) to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH(2), H(2)PO(3), NO(2), and CH(3). Although different choices for the exchange-correlation functional lead to a spread of values for the binding energy, trends across the functional groups are largely preserved for each choice, as are the final orientations of the adsorbed gas molecules. We find binding of CO(2) to exceed that of CH(4) by roughly a factor of two. However, the two gases follow very similar trends with changes in the attached functional group, despite different molecular symmetries. Our results indicate that the presence of NH(2), H(2)PO(3), NO(2), and COOH functional groups can significantly enhance gas binding, making the edges potentially viable binding sites in materials with high concentrations of edge carbons. To first order, in-plane binding strength correlates with the larger permanent and induced dipole moments on these groups. Implications for tailoring carbon structures for increased gas uptake and improved CO(2)/CH(4) selectivity are discussed.

Molecular dynamics simulations of bilayers containing mixtures of sphingomyelin with cholesterol and phosphatidylcholine with cholesterol.

We performed six molecular dynamics simulations: three on hydrated bilayers containing pure phospholipids and three on hydrated bilayers containing mixtures of these phospholipids with cholesterol. The phospholipids in our simulations were SSM (sphingomyelin containing a saturated 18:0 acyl chain), OSM (sphingomyelin with an unsaturated 18:1 acyl chain), and POPC (palmitoyloleoylphosphatidylcholine containing one saturated and one unsaturated chain). Data from our simulations were used to study systematically the effect of cholesterol on phospholipids that differed in their headgroup and tail composition. In addition to the structural analysis, we performed an energetic analysis and observed that energies of interaction between cholesterol and neighboring SM molecules are similar to the energies of interaction between cholesterol and POPC. We also observed that the interaction energy between cholesterol and neighboring lipids cannot be used for the determination of which lipids are involved in the creation of a complex.

Molecular dynamics simulations of SOPS and sphingomyelin bilayers containing cholesterol.

We performed a molecular dynamics simulation of an asymmetric bilayer that contained different lipid mixtures in its outer and inner leaflets. The outer leaflet contained a mixture of sphingomyelin (SM) with cholesterol and the inner leaflet a mixture of stearoyl-oleoyl-phosphatidylserine (SOPS) with cholesterol. For comparison purposes, we also performed two simulations on symmetric bilayers: the first simulation was performed on a bilayer containing a binary mixture of SOPS with cholesterol; the second contained a mixture of SM with cholesterol. We studied the hydrogen-bonding network of the bilayers in our simulations and the difference in the network properties in the monolayers either with SM or SOPS. We observed that in the asymmetric bilayer the properties of monolayers were the same as in the corresponding monolayers in the symmetric bilayers.

The behavior of reorientational correlation functions of water at the water-lipid bilayer interface.

We studied the effects of confinement and the head group motion on the behavior of the reorientational correlation functions for water molecules at the water/lipid bilayer interface. The correlation functions were calculated from the data obtained from two molecular dynamics simulations: one with a flexible bilayer and the other with a frozen bilayer. In our present analysis the water molecules were separated into spatial regions according to their distance from the bilayer surface and into population groups, according to the length of their stay in the corresponding regions. We estimate that for most of the water molecules that are in a strongly confined environment of the transition region between the head groups and tails, and that solvate carbonyl groups, the decay time of their reorientational correlation functions is of the order of a few tens of picoseconds. Water molecules that stay inside the transition region for long periods of time can display longer time decay (of the order of hundreds of picoseconds). This latter long time decay is determined by the dynamics of the phospholipids, it is substantially reduced when the bilayer is frozen. The decay of the correlation functions for the interfacial water molecules that are solvating the head groups is also slowed down when compared to bulk, but just by factors of 3-4.

Structure and dynamics of water at the interface with phospholipid bilayers.

We have performed two molecular-dynamics simulations to study the structural and dynamical properties of water at the interface with phospholipid bilayers. In one of the simulations the bilayer contained neutral phospholipid molecules, dioleoylphosphatidylcholine (DOPC); in the second simulation the bilayer contained charged lipid molecules, dioleoylphosphatidylserine (DOPS). From the density profile of water we observe that water next to the DOPS bilayer is more perturbed as compared to water near the DOPC bilayer. Using an energetic criterion for the determination of hydrogen bonding we find that water molecules create strong hydrogen bonds with the headgroups of the phospholipid molecules. Due to the presence of these bonds and also due to the confinement of water, the translational and orientational dynamics of water at the interface are slowed down. The degree of slowing down of the dynamics depends upon the location of water molecules near a lipid headgroup.

n-Pentane and isopentane in one-dimensional channels.

Molecular dynamics studies of n-pentane and isopentane in one-dimensional channels of AlPO(4)-5 and a carbon nanotube are reported. Variation of the structure and energetics in AlPO(4)-5 along the channel axis of isopentane is similar to what has been found for other rigid molecular systems. In n-pentane, these properties exhibit more frequent undulations along the channel due to flexibility. The end-to-end distance of n-pentane is a function of its position along the channel in AlPO(4)-5, suggesting that n-pentane has to alternately stretch in the narrow part and destretch or coil in the broader part of the channel. n-Pentane lies flat instead of upright on the inner surface of the carbon nanotube. Both of the species exhibit diffusive motion in AlPO(4)-5, and the self-diffusivity is higher than that in bulk. Isopentane has a higher diffusivity than does n-pentane. This is attributed to the higher cross section of isopentane, which is closer to the void cross section. Further, the coupling of the translational motion with the slower dihedral angle reorientation in the case of n-pentane decreases its mobility. Superdiffusive motion is seen for both species in the carbon nanotube. These results can be understood in terms of the levitation effect.