Biomedical subjects

K E Gubbins

Publications and source records attributed to K E Gubbins.

7 recordsLinked to original sources

PubMed2006

Freezing of fluids confined in a disordered nanoporous structure.

Freezing of a simple fluid in a disordered nanoporous carbon is studied using molecular simulations. Only partial crystallization occurs, and the confined phase is composed of crystalline and amorphous nanodomains. This freezing behavior departs strongly from that for nanopores of simple geometry. We present a method for analyzing the freezing in such disordered materials in terms of a transition in the average size and number of crystalline clusters. The results provide a basis for the interpretation of experiments on freezing in such materials, particularly 1H-NMR and scattering experiments.

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PubMed2005

Effect of temperature on the adsorption of water in porous carbons.

We report experimental and simulation studies to investigate the effect of temperature on the adsorption isotherms for water in carbons. Adsorption isotherms are measured by a gravimetric technique in carbon-fiber monoliths at 378 and 423 K and studied by molecular simulation in ideal carbon pores in the temperature range 298-600 K. Experimental adsorption isotherms show a gradual water uptake, as the pressure increases, and narrow adsorption-desorption hysteresis loops. In contrast, simulated adsorption isotherms at room temperature are characterized by negligible uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption-desorption hysteresis loops. As the temperature increases, the relative pressure at which pore filling occurs increases and the size of the hysteresis loop decreases. Experimental adsorption-desorption hysteresis loops are narrower than those from simulation. Discrepancies between simulation and experimental results are attributed to heterogeneities in chemical composition, pore connectivity, and nonuniform pore-size distribution, which are not accounted for in the simulation model. The hysteresis phase diagram for confined water is obtained by recording the pressure-density conditions that bound the simulated hysteresis loop at each temperature. We find that the hysteresis critical temperature, i.e., the lowest temperature at which no hysteresis is detected, can be hundreds of degrees lower than the vapor-liquid critical temperature for bulk model water. The properties of confined water are discussed with the aid of simulation snapshots and by analyzing the structure of the confined fluid.

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PubMed2005

Dissociation of water on defective carbon substrates.

Using calculations from first principles, we found that water can dissociate over defective sites in graphene or nanotubes following many possible reaction pathways, some of which have activation barriers lower than half the value for the dissociation of bulk water. This reduction is caused by spin selection rules that allow the system to remain on the same spin surface throughout the reaction.

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PubMed2005

Water in carbon nanotubes: adsorption isotherms and thermodynamic properties from molecular simulation.

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled (6:6), (8:8), (10:10), (12:12), and (20:20) carbon nanotubes in the 248-548 K temperature range. At room temperature the resulting adsorption isotherms in (10:10) and wider single-walled carbon nanotubes (SWCNs) are characterized by negligible water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of the hysteresis loops decreases as pore diameter narrows and it becomes negligible for water adsorption in (8:8) and (6:6) SWCNs. Results for the isosteric heat of adsorption, density profiles along the pore axis and across the pore radii, order parameter across the pore radii, and x-ray diffraction patterns are presented. Layered structures are observed when the internal diameter of the nanotubes is commensurate to the establishment of a hydrogen-bonded network. The structure of water in (8:8) and (10:10) SWCNs is ordered when the temperature is 298 and 248 K, respectively. By simulating adsorption isotherms at various temperatures, the hysteresis critical temperature, e.g., the lowest temperature at which no hysteresis can be detected, is determined for water adsorbed in (20:20), (12:12), and (10:10) SWCNs. The hysteresis critical temperature is lower than the vapor-liquid critical temperature for bulk Simple Point Charge-Extended (SPCE) water model.

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PubMed2005

Solid/solid phase transitions in confined thin films: a zero temperature approach.

We report a density functional theory study of confinement induced solid/solid phase transitions in a thin film (modeled as methane) at T=0. The solid film is confined by two graphite surfaces represented by a mean-field potential. As the wall separation is varied the structure of the confined film changes, which influences its density and the solvation force. Using the directly accessible grand canonical potential density we determine the stable phases and calculate the exact location of the phase transitions. We observe a series of phases having square and triangular symmetry. At low wall separations we find zig-zag buckling and an asymmetric buckled phase, whose structure is consistent with the strongest buckling instability of a triangular monolayer predicted by Chou and Nelson [Phys. Rev. E 48, 4611 (1993)] but, to our knowledge, has not been observed as a stable phase before. We find that the two-dimensional order parameters Psi(4) (square symmetry) and Psi(6) (triangular symmetry) show unphysical behavior in the transition region between square and triangular symmetry. Thus, in the present model they fail to predict the right location of the phase transitions.

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PubMed2004

Anomalous temperature dependence of surfactant self-assembly from aqueous solution.

The self-assembly of surfactant molecules from aqueous solutions exhibits anomalous and as yet unexplained temperature dependence. These effects include (a) a decrease in surfactant solubility, (b) an increase of the critical micelle concentration, and (c) increasing self-assembly on solid surfaces with increasing temperature near ambient temperature. These are the opposite of what one intuitively expects based on increasing molecular motion with temperature, and of what is observed for simpler fluids. Using a lattice gas theory that allows for inhomogeneity, hydrogen bonding, and micelle formation, we show conclusively that all of these phenomena arise from hydrogen bonding between water and the surfactant headgroups. While theory and experiment show very good qualitative agreement when such H bonding is included, its omission leads to complete reversal of the temperature dependence.

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PubMed2003

Molecular dynamics simulations of simple fluids confined in realistic models of nanoporous carbons.

We present molecular dynamics simulations in the micro-canonical ensemble of a Lennard-Jones model of nitrogen confined in realistic models for saccharose-based carbons developed in our previous work. We calculate the velocity autocorrelation function and mean-squared displacement, and the self-diffusivities from the latter. We observe that the self-diffusivity increases with temperature and exhibits a maximum with loading or adsorbate density. To the best of our knowledge, a maximum in self-diffusivities has not been observed in molecular dynamics simulations of fluids confined in slit pores.

Computer Simulation↗