Oleg Shklyaev

Cellulose Microfibril Twist, Mechanics, and Implication for Cellulose Biosynthesis

All-atom molecular dynamics simulations with explicit water solvent were used to investigate the microstructure and conformational dynamics of cellulose Iβ microfibrils as a function of microfibril length and cross-sectional size and shape. Cellulose microfibrils quickly develop a right-handed twist, which then remains stable over the entire 10 ns simulation time. The helical angle is independent of microfibril length and inversely proportional to its cross-sectional area, in accord with the expectations of continuum theory for an intrinsic chiral twist that is opposed by torsional shear. These calculations provide-to our knowledge-the first estimates of the shear modulus of a cellulose microfibril from MD simulations. The internal strains caused by this helical twist, propagated indefinitely along the microfibril axis, could be relaxed by periodic regions of amorphous structure along the axis of the cellulose microfibrils.

Stability of an evaporating thin liquid film

We use a newly developed set of interface conditions to revisit the problem of an evaporating thin liquid film. In particular, instead of the conventional Hertz-Knudsen-Langmuir equation for the evaporation mass flux, we impose a more general equation expressing the balance of configurational momentum. This balance, which supplements the conventional conditions enforcing the balances of mass, momentum and energy on the film surface, arises from a consideration of configurational forces within a thermodynamical framework. We study the influence of two newly introduced terms on the evolution of the liquid film. One of these terms accounts for the transport of energy within the liquid-vapour interface. The other term, which we refer to as the effective pressure, accounts for vapour recoil. Both new terms are found to be stabilizing. Furthermore, the effective pressure is found to affect a time-dependent base state of the evaporating film and to be an important factor in applications involving liquid films with thicknesses of one or two monolayers. Specifically, we demonstrate that consideration of the effective pressure makes it possible to observe the influence of the van der Waals interactions on film evolution close to the instant of rupture. Dimensional considerations indicate that one of the most significant influences of these effects occurs for molten metals.

Modeling electrostatically induced collapse transitions in carbon nanotubes.

Molecular dynamics simulations demonstrate how a mechanically bistable single-walled carbon nanotube can act as a variable-shaped capacitor. If the voltage is tuned so that collapsed and inflated states are degenerate, the tubes susceptibility to diverse external stimuli--temperature, voltage, trapped atoms--diverges following a universal curve, yielding an exceptionally sensitive sensor or actuator. The boundary between collapsed and inflated states can shift hundreds of angstroms in response to a single gas atom inside the tube. Several potential nanoelectromechanical devices could be based on this electrically tuned crossover between near-degenerate collapsed and inflated configurations.

Constraints on {\rm I}\beta cellulose twist from DFT calculations of ^{13}\hbox {C} NMR chemical shifts

We investigate theoretically the NMR response of twisted configurations of Iβ\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}

Adsorption-induced shape transitions in bistable nanopores with atomically thin walls

{\rm I}\beta

Convective Self-Sustained Motion in Mixtures of Chemically Active and Passive Particles

\end{document} cellulose in the tg conformation. These finite helical angle structures were constructed by a mathematical deformation of zero-angle configurations obtained via the periodic density functional energy minimizations with dispersion corrections (DFT-D2). Subsequent calculations of the 13C\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}

Theory of carbomorph cycles.

{^{13}\hbox {C}}