Lysozyme adsorption on polyethylene surfaces: why are long simulations needed?

The adsorption of lysozyme onto a polyethylene (PE) surface in an aqueous environment was investigated via molecular dynamics (MD) simulation. The adsorption can be divided into three processes: diffusion to the surface, dehydration induced by hydrophobic surface-protein interactions, and denaturation. The dehydration process is very long, around 70 ns. Structural deformations start soon after the protein reaches the surface and continue during the whole trajectory. The hydrophobic residues are slowly driven toward the surface, inducing changes in the protein's secondary structure. The protein's secondary structural components near the surface are more disturbed than those farther away from the surface. The lysozyme is adsorbed with its long axis parallel to the surface and displays an anisotropic mobility on the surface that is probably due to the intrinsic structure of the PE surface. Our study demonstrates the need for long-time atomistic simulation in order to gain a complete understanding of the adsorption process.     

A High Token Indicativity Account of Knowledge

In this paper, I provide a probabilistic account of factual knowledge, based on the notion of chance, which is a function of an event (or a fact — I will use ‘fact’ to cover both) given a prior history. This account has some affinity with my chance account of token causation, but it neither relies on it nor presupposes it. Here, I concentrate on the core cases of perceptual knowledge and of knowledge by memory (based on perception). (The account can be extended to the other modes of knowledge, but not in this paper.) The analysis of knowledge presented below is externalist. The underlying intuition guiding the treatment of knowledge in this paper is that knowledge boils down to high token discriminative indicativeness. Type indicativeness or type discriminability are neither necessary nor sufficient for knowledge: the token aspect comes out in the strong dependence on the specific circumstances and chances of the case. The main condition of the first section, the indicativity condition (KI), properly refined, yields pertinent (token) indicativity as a main constituent. Very roughly, it involves the chance of the content clause p being higher given the subject's believing that p than otherwise. The discriminability condition in question (section 3) captures the sense of discriminability appropriate for knowledge and yield the indicativity condition: it is an extension of the indicativity condition KI. Roughly, the subject’s ability to discriminate the object in front of her being red from its being green is captured by holding fixed, in the indicativity condition, the condition “the object in front of her is red or green.” A major element in the analysis is the so-called Contrast Class, which governs the scope of discriminability. This is the class of features that have to be taken into account in the discriminability condition, and it is characterized by two constraints. Very roughly, according to the first constraint, for a feature to be in the contrast class, it must not represent a sub-type of (the feature specified by) the predicate in the content clause. According to the second constraint, which is a central condition with many implications, the chance that the object specified in the content clause has a feature represented in the contrast class must not under the circumstances be too low. This constraint, within the framework of the discriminability condition, brings out a major constitutive aspect of knowledge: knowledge amounts to a limited vulnerability to mistakes of the belief in question under the circumstances at hand. The contrast class plays a major role in my treatment of skepticism. The second constraint on the Contrast Class together with the VHP condition below bring out precisely the way in which perceptual knowledge is fallible.     

A Case Study of a Non-Compensatory Approach to Ranking Transportation Projects

This paper examines the use of a concordance-type model for prioritizing transportation projects. In the particular case examined, multiple criteria are involved, and projects can be rated only on a qualitative basis. The model augments the well-known ELECTRA methodology with a tournament ranking procedure. The resulting procedure, known as SELECTRA, is presently being used to rank order over 200 investment projects within the Ontario Ministry of Transportation and Communications.     

Polymer‐regulated pattern formation in pseudo‐2D arrays of a fullerene derivative at the solution—Air interface

Self‐assembly of nanoparticles (NPs) into nonclose‐packed (ncp), semi‐two‐dimensional (2D) arrays is of interest in a variety of applications. Of special interest are photochemically active surfactant‐like fullerene derivatives [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM). The study presented here characterizes the morphology and structure of patterns formed by a mixture of PCBM NP and an amphiphilic block‐copolymer tethered at the water–air interface (a surface brush) as a function of the concentration of poly(ethylene oxide) (PEO) dissolved in the liquid subphase. Theoretical modeling of the system shows that the concentration of PEO in the subphase mediates the dimensions of the surface brush and at high PEO concentrations induces a collapse of the brush at the solution–air interface. The state of the surface brush is suggested to tune the semi‐2D patterns observed in the experiments via lateral depletion interactions and, in particular, induce lateral phase separation of the PCBM‐block copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Realizing optical magnetism from dielectric metamaterials

We demonstrate, for the first time, an all-dielectric metamaterial composite in the midinfrared based on micron-sized, high-index tellurium dielectric resonators. Dielectric resonators are desirable compared to conventional metallodielectric metamaterials at optical frequencies as they are largely angular invariant, free of Ohmic loss, and easily integrated into three-dimensional volumes. Measurements and simulation provide evidence of optical magnetism, which could be used for infrared magnetic mirrors, hard or soft surfaces, and subwavelength cavities.     

Time dependence of lysozyme adsorption on end-grafted polymer layers of variable grafting density and length

A combined experimental and theoretical approach establishes the long-lived nature of protein adsorption on surfaces coated with chemically grafted macromolecules. Specifically, we monitor the time dependence of adsorption of lysozyme on surfaces comprising polymer assemblies made of poly(2-hydroxyethyl methacrylate) brushes grafted onto flat silica surfaces such that they produce patterns featuring orthogonal and gradual variation of the chain length (N) and grafting density (σ). We show that in the kinetically controlled regime, the amount of adsorbed protein scales universally with the product σN, while at equilibrium the amount of adsorbed protein is governed solely by σ. Surprisingly, for moderate concentrations of protein in solution, adsorption takes more than 72 h to reach an equilibrium, or steady state. Our experimental findings are corroborated with predictions using molecular theory that provides further insight into the protein adsorption phenomenon. The theory predicts that the universal behavior observed experimentally should be applicable to polymers in poor and theta solvents and to a limited extent also to good solvent conditions. Our combined experimental and theoretical findings reveal that protein adsorption is a long-lived phenomenon, much longer than generally assumed. Our studies confirm the previously predicted important differences in behavior for the kinetic versus thermodynamic control of protein adsorption.     

Cluster structure and corralling effect driven by interaction mismatch in two dimensional mixtures

The formation of clusters with crystal-like order in two dimensions is studied using Monte Carlo simulations. We find that the necessary conditions to induce the formation of clusters of one component is to add a second component that has a larger size and that has a long-range soft repulsive interaction with its own kind but not with the other one. The clusters of the small particles are found to be surrounded by a network of quasi-one-dimensional arrangements of the larger particles. The degree of order of the clusters is found to depend on the concentration of the larger particles. The findings explain recent experimental observations on lipid-poloxamer mixtures and they provide guidelines for how to form ordered clusters of nanoparticles in two dimensions.     

Flow-induced control of chemical turbulence

We report spatiotemporal chaos in the Oregonator model of the Belousov-Zhabotinsky reaction. Spatiotemporal chaos spontaneously develops in a regime, where the underlying local dynamics show stable limit cycle oscillations (diffusion-induced turbulence). We show that spatiotemporal chaos can be suppressed by a unidirectional flow in the system. With increasing flow velocity, we observe a transition scenario from spatiotemporal chaos via a regime of travelling waves to a stationary steady state. At large flow velocities, we recover the known regime of flow distributed oscillations.