Segue between favorable and unfavorable solvation

Solvation of small and large clusters are studied by simulation, considering a range of solvent-solute attractive energy strengths. Over a wide range of conditions, both for solvation in the Lennard-Jones liquid and in the SPC model of water, it is shown that the mean solvent density varies linearly with changes in solvent-solute adhesion or attractive energy strength. This behavior is understood from the perspective of Weeks' theory of solvation (Annu. Rev. Phys. Chem. 2002, 53, 533) and supports theories based upon that perspective.     

Sources of diversity in bactobolin biosynthesis by Burkholderia thailandensis E264

A series of deletion mutants in the recently identified bactobolin biosynthetic pathway defined the roles of several key biosynthetic enzymes and showed how promiscuity in three enzyme systems allows this cluster to produce multiple products. Studies on the deletion mutants also led to four new bactobolin analogs that provide additional structure-activity relationships for this interesting antibiotic family.     

An improved coarse-grained model of solvation and the hydrophobic effect

We present a coarse-grained lattice model of solvation thermodynamics and the hydrophobic effect that implements the ideas of Lum-Chandler-Weeks theory [J. Phys. Chem. B 134, 4570 (1999)] and improves upon previous lattice models based on it. Through comparison with molecular simulation, we show that our model captures the length-scale and curvature dependence of solvation free energies with near-quantitative accuracy and 2-3 orders of magnitude less computational effort, and further, correctly describes the large but rare solvent fluctuations that are involved in dewetting, vapor tube formation, and hydrophobic assembly. Our model is intermediate in detail and complexity between implicit-solvent models and explicit-water simulations.     

Fluorescent one-dimensional nanostructures from a group of uniform materials based on organic salts

Herein we report the synthesis of a fluorescent organic salt through anion exchange and the subsequent fabrication of 1D-nanostructures via a facile templating method.     

Condition number estimates for combined potential integral operators in acoustics and their boundary element discretisation

We consider the classical coupled, combined‐field integral equation formulations for time‐harmonic acoustic scattering by a sound soft bounded obstacle. In recent work, we have proved lower and upper bounds on the L² condition numbers for these formulations and also on the norms of the classical acoustic single‐ and double‐layer potential operators. These bounds to some extent make explicit the dependence of condition numbers on the wave number k, the geometry of the scatterer, and the coupling parameter. For example, with the usual choice of coupling parameter they show that, while the condition number grows like k^1/3 as k →∞, when the scatterer is a circle or sphere, it can grow as fast as k^7/5 for a class of “trapping” obstacles. In this article, we prove further bounds, sharpening and extending our previous results. In particular, we show that there exist trapping obstacles for which the condition numbers grow as fast as exp(γk), for some γ > 0, as k →∞ through some sequence. This result depends on exponential localization bounds on Laplace eigenfunctions in an ellipse that we prove in the appendix. We also clarify the correct choice of coupling parameter in 2D for low k. In the second part of the article, we focus on the boundary element discretisation of these operators. We discuss the extent to which the bounds on the continuous operators are also satisfied by their discrete counterparts and, via numerical experiments, we provide supporting evidence for some of the theoretical results, both quantitative and asymptotic, indicating further which of the upper and lower bounds may be sharper. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2010     

Preparation and relaxation of very stable glassy states of a simulated liquid

We prepare metastable glassy states in a model glass former made of Lennard-Jones particles by sampling biased ensembles of trajectories with low dynamical activity. These trajectories form an inactive dynamical phase whose "fast" vibrational degrees of freedom are maintained at thermal equilibrium by contact with a heat bath, while the "slow" structural degrees of freedom are located in deep valleys of the energy landscape. We examine the relaxation to equilibrium and the vibrational properties of these metastable states. The glassy states we prepare by our trajectory sampling method are very stable to thermal fluctuations and also more mechanically rigid than low-temperature equilibrated configurations.     

Kinetic evaluation of highly active supported gold catalysts prepared from monolayer-protected clusters: an experimental Michaelis-Menten approach for determining the oxygen binding constant during CO oxidation catalysis

Thiol monolayer-protected Au clusters (MPCs) were prepared using dendrimer templates, deposited onto a high-surface-area titania, and then the thiol stabilizers were removed under H2/N2. The resulting Au catalysts were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy of adsorbed CO. The Au catalysts prepared via this route displayed minimal particle agglomeration during the deposition and activation steps. Structural data obtained from the physical characterization of the Au catalysts were comparable to features exhibited from a traditionally prepared standard Au catalyst obtained from the World Gold Council (WGC). A differential kinetic study of CO oxidation catalysis by the MPC-prepared Au and the standard WGC catalyst showed that these two catalyst systems have essentially the same reaction order and Arrhenius apparent activation energies (28 kJ/mol). However, the MPC-prepared Au catalyst shows 50% greater activity for CO oxidation. Using a Michaelis-Menten approach, the oxygen binding constants for the two catalyst systems were determined and found to be essentially the same within experimental error. To our knowledge, this kinetic evaluation is the first experimental determination of oxygen binding by supported Au nanoparticle catalysts under working conditions. The values for the oxygen binding equilibrium constant obtained from the Michaelis-Menten treatment (ca. 29-39) are consistent with ultra-high-vacuum measurements on model catalyst systems and support density functional theory calculations for oxygen binding at corner or edge atoms on Au nanoparticles and clusters.     

Adjoint algorithms for the Navier–Stokes equations in the low Mach number limit

This paper describes a derivation of the adjoint low Mach number equations and their implementation and validation within a global mode solver. The advantage of using the low Mach number equations and their adjoints is that they are appropriate for flows with variable density, such as flames, but do not require resolution of acoustic waves. Two versions of the adjoint are implemented and assessed: a discrete-adjoint and a continuous-adjoint. The most unstable global mode calculated with the discrete-adjoint has exactly the same eigenvalue as the corresponding direct global mode but contains numerical artifacts near the inlet. The most unstable global mode calculated with the continuous-adjoint has no numerical artifacts but a slightly different eigenvalue. The eigenvalues converge, however, as the timestep reduces. Apart from the numerical artifacts, the mode shapes are very similar, which supports the expectation that they are otherwise equivalent. The continuous-adjoint requires less resolution and usually converges more quickly than the discrete-adjoint but is more challenging to implement. Finally, the direct and adjoint global modes are combined in order to calculate the wavemaker region of a low density jet.