By means of molecular dynamics simulations we study the structure and dynamics of water molecules in contact with a model hydrophobic surface: a planar graphene-like layer. The analysis of the distributions of a local structural index indicates that the water molecules proximal to the graphene layer are considerably more structured than the rest and, thus, than the bulk. This structuring effect is lost in a few angstroms and is basically independent of temperature for a range studied comprising parts of both the normal liquid and supercooled states (240K to 320K). In turn, such structured water molecules present a dynamics that is slower than the bulk, as a consequence of their improved interactions with their first neighbors.

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Soluble proteins must maintain backbone hydrogen bonds (BHBs) water-tight to ensure structural integrity. This protection is often achieved by burying the BHBs or wrapping them through intermolecular associations. On the other hand, water has low coordination resilience, with loss of hydrogen-bonding partnerships carrying significant thermodynamic cost. Thus, a core problem in structural biology is whether natural design actually exploits the water coordination stiffness to seal the backbone in regions that are exposed to the solvent. This work explores the molecular design features that make this type of seal operative, focusing on the side-chain arrangements that shield the protein backbone. We show that an efficient sealing is achieved by adapting the sub-nanoscale surface topography to the stringency of water coordination: an exposed BHB may be kept dry if the local concave curvature is small enough to impede formation of the coordination shell of a penetrating water molecule. Examination of an exhaustive database of uncomplexed proteins reveals that exposed BHBs invariably occur within such sub-nanoscale cavities in native folds, while this level of local ruggedness is absent in other regions. By contrast, BHB exposure in misfolded proteins occurs with larger local curvature promoting backbone hydration and consequently, structure disruption. These findings unravel physical constraints fitting a spatially dependent least-action for water coordination, introduce a molecular design concept, and herald the advent of water-tight peptide-based materials with sufficient backbone exposure to remain flexible.

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This work addresses the cyclic scheduling of cracking furnace shutdowns in ethylene plants within a shortterm production planning model, based on a discrete time representation. Cracking furnaces are continuous parallel reactors that show decaying performance during their operation due to coke deposition on coil walls. For that reason, they must be periodically shutdown and cleaned. This behavior is modeled through binary variables and coil internal roughness, a variable whose increase has a linear dependence on operation time. After cleanup, roughness is at its lowest value and starts increasing again during operation. The cyclic scheduling model includes not only furnaces models but an entire plant mathematical model at each time interval to carry out production planning for meeting varying demands, as well as to determine main plant operating variable profiles and to predict an ethane recycle stream, which is an important feed to cracking furnaces and constitutes a key variable for the optimal shutdown schedule. The model includes nonlinear mathematical functions for each cracking furnace production as a function of main process variables, simplified models for distillation columns in the separation train, and raw material and product storage equations. Additional binary variables are included to force null values for production in shutdown furnaces. The resulting mixed-integer nonlinear programming (MINLP) model is solved in GAMS with DICOPT++.

By means of molecular dynamics simulations we analyze the behavior of water in contact with model hydrophobic cavities and tunnels. We study the hydration and filling propensity of cavities and tunnels carved in alkane monolayers and, for comparison, we also study single-walled carbon nanotubes of similar size. Our results will determine the dependence of the filling propensity as a function of cavity size while revealing the dynamical nature of the process with alternation of filled and dry states. Concerning the tunnels built across the monolayer, we shall show that the minimum diameter in order to get filled is about twice as large as that for the carbon nanotubes, thus evidencing a more hydrophobic behavior. The existence of water-water hydrogen bonds, a necessary condition for penetration, will also be made evident.

Dynamics in glass-forming liquids in the supercooled regime vary considerably from one point of the sample to another suggesting the existence of regions with different degrees of jamming. In fact, the existence of relatively compact regions with particles with an enhanced propensity for motion has been detected in model glassy systems. In turn, the structural relaxation has been shown to be accomplished by means of a series of fast transitions between metabasins in the potential energy landscape involving the collective motion of a substantial number of particles arranged in relatively compact clusters (democratic clusters or d clusters). In this work we shall complete this picture by identifying the connections between local structural jamming, metabasin confining strength, and d clusters. Thus we shall demonstrate that the degree of jamming of the local structure dictates the confining strength of the local metabasin and that the local high propensity regions and the d clusters are not only similar in nature but that they share a significant amount of particles.