Stereocontrolled approaches to substituted tetrahydrofuran and cis-hydrindene derivatives via cyclohexadiene-Fe(CO)3 complexes

Oxidative cyclisation of the diol complex (6) followed by removal of Fe(CO)₃ gives a single tetrahydrofuran derivative (7). Intramolecular nucleophile reaction of the salt (13) leads to cis-hydrindene derivative (14).     

A Hydrogel Vitreous Substitute that Releases Antioxidant

Current experimental vitreous substitutes only replace the physical functions of the natural vitreous humor. Removal of the native vitreous disrupts oxygen homeostasis in the eye, causing oxidative damage to the lens that likely results in cataract formation. Neither current clinical treatments nor other experimental vitreous substitutes consider the problem of oxidative stress after vitrectomy. To address this problem, biomimetic hydrogels are prepared by free radical polymerization of poly(ethylene glycol) methacrylate and poly(ethylene glycol) diacrylate. These hydrogels have similar mechanical and optical properties to the vitreous. The hydrogels are injectable through small‐gauge needles and demonstrate in vitro biocompatibility with human retinal and lens epithelial cells. The hydrogels and added vitamin C, an antioxidant, show a synergistic effect in protecting ocular cells against reactive oxygen species, which fulfills a chemical function of the natural vitreous. These hydrogels have the potential to prevent post‐vitrectomy cataract formation and reduce the cost of additional surgeries.     

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.     

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     

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.     

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.