Wall mediated transport in confined spaces: Exact theory for low density

We present a theory for the transport of molecules adsorbed in slit and cylindrical nanopores at low density, considering the axial momentum gain of molecules oscillating between diffuse wall reflections. Good agreement with molecular dynamics simulations is obtained over a wide range of pore sizes, including the regime of single-file diffusion where fluid-fluid interactions are shown to have a negligible effect on the collective transport coefficient. We show that dispersive fluid-wall interactions considerably attenuate transport compared to classical hard sphere theory

Configurational Temperature, Verification of Monte Carlo Simulations

[Unable to convert symbols, please look at PDF version for symbols] A new diagnostic that is useful for checking the algorithmic correctness of Monte Carlo computer programs is presented. The check is made by comparing the Boltzmann temperature, which is input to the program and used to accept or reject moves, with a configurational temperature k T B config [unable to convert symbol, please see PDF]. Here, F is the potential energy of the system and [symbal]represents the dimensionless gradient operator with respect to the particle positions [symbol]. We show, using a simulation of Lennard-Jones particles, that the configurational temperature rapidly and accurately tracks changes made to the input temperature even when the system is not in global thermodynamic equilibrium. Coding and/or algorithmic errors can be detected by checking that the input temperature and Tconfig agree. The effects of system size and continuity of F and its first derivative on Tconfig are also discussed

The fluctuation theorem and Lyapunov weights

The Fluctuation Theorem (FT) is a generalisation of the Second Law of Thermodynamics that applies to small systems observed for short times. For thermostatted systems it gives the probability ratio that entropy will be consumed rather than produced. In this paper we derive the Transient and Steady State Fluctuation Theorems using Lyapunov weights rather than the usual Gibbs weights. At long times the Fluctuation Theorems so derived are identical to those derived using the more standard Gibbs weights.Comment: 26 pages; to appear in Physica

Measuring Nonequilibrium Temperature of Forced Oscillators

The meaning of temperature in nonequilibrium thermodynamics is considered by using a forced harmonic oscillator in a heat bath, where we have two effective temperatures for the position and the momentum, respectively. We invent a concrete model of a thermometer to testify the validity of these different temperatures from the operational point of view. It is found that the measured temperature depends on a specific form of interaction between the system and a thermometer, which means the zeroth law of thermodynamics cannot be immediately extended to nonequilibrium cases.Comment: 8 page

O(N)O(N) fluctuations and lattice distortions in 1-dimensional systems

Statistical mechanics harmonizes mechanical and thermodynamical quantities, via the notion of local thermodynamic equilibrium (LTE). In absence of external drivings, LTE becomes equilibrium tout court, and states are characterized by several thermodynamic quantities, each of which is associated with negligibly fluctuating microscopic properties. Under small driving and LTE, locally conserved quantities are transported as prescribed by linear hydrodynamic laws, in which the local material properties of the system are represented by the transport coefficients. In 1-dimensional systems, on the other hand, the transport coefficients often appear to depend on the global state, rather than on the local state of the system at hand. We interpret these facts within the framework of boundary driven 1-dimensional Lennard-Jones chains of $N$ oscillators, observing that they experience non-negligible $O(N)$ lattice distortions and fluctuations. This implies that standard hydrodynamics and certain expressions of energy flow do not apply in these cases. One possible modification of the energy flow is considered.Comment: 8 pages, 7 figure

Tractable molecular theory of transport of Lennard-Jones fluids in nanopores

We present here a tractable theory of transport of simple fluids in cylindrical nanopores, which is applicable over a wide range of densities and pore sizes. In the Henry law low-density region the theory considers the trajectories of molecules oscillating between diffuse wall collisions, while at higher densities beyond this region the contribution from viscous flow becomes significant and is included through our recent approach utilizing a local average density model. The model is validated by means of equilibrium as well nonequilibrium molecular dynamics simulations of supercritical methane transport in cylindrical silica pores over a wide range of temperature, density, and pore size. The model for the Henry law region is exact and found to yield an excellent match with simulations at all conditions, including the single-file region of very small pore size where it is shown to provide the density-independent collective transport coefficient. It is also shown that in the absence of dispersive interactions the model reduces to the classical Knudsen result, but in the presence of such interactions the latter model drastically overpredicts the transport coefficient. For larger micropores beyond the single-file region the transport coefficient is reduced at high density because of intermolecular interactions and hindrance to particle crossings leading to a large decrease in surface slip that is not well represented by the model. However, for mesopores the transport coefficient increases monotonically with density, over the range studied, and is very well predicted by the theory, though at very high density the contribution from surface slip is slightly overpredicted. It is also seen that the concept of activated diffusion, commonly associated with diffusion in small pores, is fundamentally invalid for smooth pores, and the apparent activation energy is not simply related to the minimum pore potential or the adsorption energy as generally assumed. (C) 2004 American Institute of Physics

MicroRNA-153 targeting of KCNQ4 contributes to vascular dysfunction in hypertension.

AIMS: Kv7.4, a voltage-dependent potassium channel expressed throughout the vasculature, controls arterial contraction and is compromised in hypertension by an unknown mechanism. MicroRNAs (miRs) are post-transcriptional regulators of protein production and are altered in disease states such as hypertension. We investigated whether miRs regulate Kv7.4 expression. METHODS AND RESULTS: In renal and mesenteric arteries (MAs) of the spontaneously hypertensive rat (SHR), Kv7.4 protein decreased compared with the normotensive (NT) rat without a decrease in KCNQ4 mRNA, inferring that Kv7.4 abundance was determined by post-transcriptional regulation. In silico analysis of the 3' UTR of KCNQ4 revealed seed sequences for miR26a, miR133a, miR200b, miR153, miR214, miR218, and let-7d with quantitative polymerase chain reaction showing miR153 increased in those arteries from SHRs that exhibited decreased Kv7.4 levels. Luciferase reporter assays indicated a direct targeting effect of miR153 on the 3' UTR of KCNQ4. Introduction of high levels of miR153 to MAs increased vascular wall thickening and reduced Kv7.4 expression/Kv7 channel function compared with vessels receiving a non-targeting miR, providing a proof of concept of Kv7.4 regulation by miR153. CONCLUSION: This study is the first to define a role for aberrant miR153 contributing to the hypertensive state through targeting of KCNQ4 in an animal model of hypertension, raising the possibility of the use of miR153-related therapies in vascular disease