Oxidative Deselenization of Selenocysteine: Applications for Programmed Ligation at Serine

Despite the unique chemical properties of selenocysteine (Sec), ligation at Sec is an under‐utilized methodology for protein synthesis. We describe herein an unprecedented protocol for the conversion of Sec to serine (Ser) in a single, high‐yielding step. When coupled with ligation at Sec, this transformation provides a new approach to programmed ligations at Ser residues. This new reaction is compatible with a wide range of functionality, including the presence of unprotected amino acid side chains and appended glycans. The utility of the methodology is demonstrated in the rapid synthesis of complex glycopeptide fragments of the epithelial glycoproteins MUC5AC and MUC4 and through the total synthesis of the structured, cysteine (Cys)‐free protein eglin C.     

Estimates for low-frequency elastic scattering by a rigid body

When a plane elastic wave is scattered by a rigid body the surface integral of the traction, projected along the direction of polarization of the incident wave, provides the leading low-frequency approximation for the scattering amplitudes. Two kinds of lower and upper bounds for the surface traction integral are given. One is based on the geometrical characteristics of the scatterer and is expressed in terms of corresponding values of the best fitting interior and exterior confocal triaxial ellipsoids. The case of best fitting interior and exterior spheres is examined as a special case. These bounds are sharp in the sense that they both become equalities when the scatterer degenerates to an ellipsoid. The other kind of lower and upper bounds involve the capacity of the scatterer. All estimates were obtained by using the generalized Dirichlet and Thomson Principles of Potential Theory in Elastostatics. Furthermore, all constants appearing in the bounds are given in terms of the ratio of the phase velocities for the transverse and the longitudinal wave. An upper bound for scattering by a cube at normal incidence is also included.This work was done while both authors were visiting the Department of Mathematics of The University of Tennessee at Knoxville. The second author wishes to acknowledge partial support from The University of Tennessee Science Alliance.     

Developments in electrochemical processes for recycling lead–acid batteries

The lead–acid battery recycling industry is very well established, but the conventional pyrometallurgical processes are far from environmentally benign. Hence, recent developments of lead–acid battery recycling technologies have focused on low-temperature (electro)hydrometallurgical processes, the subject of this review, covering modified electrolytes, improved reaction engineering, better reactor design and control of operating conditions.     

Natural bond orbital analysis in the ONETEP code: Applications to large protein systems

First principles electronic structure calculations are typically performed in terms of molecular orbitals (or bands), providing a straightforward theoretical avenue for approximations of increasing sophistication, but do not usually provide any qualitative chemical information about the system. We can derive such information via post‐processing using natural bond orbital (NBO) analysis, which produces a chemical picture of bonding in terms of localized Lewis‐type bond and lone pair orbitals that we can use to understand molecular structure and interactions. We present NBO analysis of large‐scale calculations with the ONETEP linear‐scaling density functional theory package, which we have interfaced with the NBO 5 analysis program. In ONETEP calculations involving thousands of atoms, one is typically interested in particular regions of a nanosystem whilst accounting for long‐range electronic effects from the entire system. We show that by transforming the Non‐orthogonal Generalized Wannier Functions of ONETEP to natural atomic orbitals, NBO analysis can be performed within a localized region in such a way that ensures the results are identical to an analysis on the full system. We demonstrate the capabilities of this approach by performing illustrative studies of large proteins—namely, investigating changes in charge transfer between the heme group of myoglobin and its ligands with increasing system size and between a protein and its explicit solvent, estimating the contribution of electronic delocalization to the stabilization of hydrogen bonds in the binding pocket of a drug‐receptor complex, and observing, in situ, the n → π* hyperconjugative interactions between carbonyl groups that stabilize protein backbones. © 2012 Wiley Periodicals, Inc.     

Semiconductor Quantum Dots as Components of Photoactive Supramolecular Architectures

Luminescent quantum dots (QDs) are colloidal semiconductor nanocrystals consisting of an inorganic core covered by a molecular layer of organic surfactants. Although QDs have been known for more than thirty years, they are still attracting the interest of researchers because of their unique size-tunable optical and electrical properties arising from quantum confinement. Moreover, the controlled decoration of the QD surface with suitable molecular species enables the rational design of inorganic-organic multicomponent architectures that can show a vast array of functionalities. This minireview highlights the recent progress in the use of surface-modified QDs – in particular, those based on cadmium chalcogenides – as supramolecular platforms for light-related applications such as optical sensing, triplet photosensitization, photocatalysis and phototherapy.     

Net Charge Fluctuation and String Fragmentation

We present the simulation results of the net charge fluctuation in Au Au collisions at √Snn=130 GeV from a dynamic model, JPCIAE, and its revisions. The simulations are done for the quark-gluon matter, the directly produced pions, the pion matter, and the hadron matter. The simulated net charge fluctuation of the quark-gluon matter is close to the thermal model prediction for the quark-gluon gas. However, the discrepancy exists comparing the simulated net charge fluctuation for directly produced pions and the pion matter with the thermal model prediction for pion gas and the resonance pion gas, respectively. The net charge fluctuation of hadron matter from default JPCIAE simulations is nearly 3.5 times larger than quark-gluon matter. A discussion is given for the net charge fluctuation as an evidence of QGP phase transition.