Surface functionalized silica as a toolkit for studying aqueous phase palladium adsorption and mineralization on thiol moiety in the absence of external reducing agents

Biological templates such as virions or protein assemblies have several surface functional groups that can complicate the elucidation of the fundamental mechanism(s) governing the sorption and mineralization of metals on the surface of the template. Surface functionalized silica nanoclusters with hydroxyl, amine, or thiol groups serve as surrogates for understanding the interaction between individual amino acid functionalities and inorganic precursors. Analysis of palladium ion uptake on the functionalized silica enabled the investigation of a new palladium mineralization strategy using thiol surface moieties in the absence of external reducing agents. This study reveals the nature of the palladium-thiol interaction and the resulting self-reduction mechanism that produces the metal palladium nanolayer on the thiol-terminated silica. This surface functionalized silica approach is thus an effective toolkit for exploring the fundamentals of metal precursor sorption on surface functional groups, and for developing new metal deposition methodologies.     

Kinetics of congruent vaporization of ZnO islands

We examine the congruent vaporization of ZnO islands using in?situ transmission electron microscopy. Correlating quantitative measurements with a theoretical model offers a comprehensive understanding of the equilibrium conditions of the system, including equilibrium vapor pressure and surface free energy. Interestingly, the surface energy depends on temperature, presumably due to a charged surface at our specific condition of low P and high T. We find that the vaporization temperature decreases with decreasing system size, a trend that is more pronounced at higher T. Applying our results of island decay towards the growth of the ZnO provides new insights into the cooperative facet growth of anisotropic nanocrystals.     

From CCSD(T)/aug-cc-pVTZ-J to CCSD(T) complete basis set limit isotropic nuclear magnetic shieldings via affordable DFT/CBS calculations

It is shown that a linear correlation exists between nuclear shielding constants for nine small inorganic and organic molecules (N(2), CO, CO(2), NH(3), CH(4), C(2)H(2), C(2)H(4), C(2)H(6) and C(6)H(6)) calculated with 47 methods (42 DFT methods, RHF, MP2, SOPPA, SOPPA(CCSD), CCSD(T)) and the aug-cc-pVTZ-J basis set and corresponding complete basis set results, estimated from calculations with the family of polarization-consistent pcS-n basis sets. This implies that the remaining basis set error of the aug-cc-pVTZ-J basis set is very similar in DFT and CCSD(T) calculations. As the aug-cc-pVTZ-J basis set is significantly smaller, CCSD(T)/aug-cc-pVTZ-J calculations allow in combination with affordable DFT/pcS-n complete basis set calculations the prediction of nuclear shieldings at the CCSD(T) level of nearly similar accuracy as those, obtained by fitting results obtained from computationally demanding pcS-n calculations at the CCSD(T) limit. A significant saving of computational efforts can thus be achieved by scaling inexpensive CCSD(T)/aug-cc-pVTZ-J calculations of nuclear isotropic shieldings with affordable DFT complete basis set limit corrections.     

DFT calculations of structures, 13C NMR chemical shifts,and Raman RBM mode of simple models of small‐diameter zigzag (4,0) carboxylated single‐walled carbon nanotubes

Linearly conjugated benzene rings (acenes), belt‐shaped molecules (cyclic acenes), and models of single‐walled carbon nanotubes (SWCNTs) with one carboxylic group at the open end were fully optimized at the B3LYP/6‐31G* level of theory. These models were selected to obtain some insight into the nuclear isotropic changes resulting from systematically increasing the basic building units of open‐tip‐monocarboxylated SWCNTs. In addition, the position of radial breathing mode (RBM), empirically correlated with the SWCNT diameter, was directly related with the radius of model cyclic acene rings. A regular convergence of selected structural, NMR, and Raman parameters with the molecular system size increase was observed, and a simple two‐parameter mathematical formula enabled their estimation in infinity. The predicted ¹³C NMR chemical shifts of carbon atoms close to the substituted rim of carboxylated models of zigzag (4,0) SWCNTs differed significantly from the pristine nanotubes. Copyright © 2012 John Wiley & Sons, Ltd.     

Advanced Optimal Feedback Control for Tracking of Real-Life Applications

Calculating the open–loop solution of an optimal control problem is just the first step to cope with the practical realization of real life applications. Feedback controllers, like the classical Linear Quadratic Regulator (LQR), are needed to compensate pertubations appearing in reality. Although these controllers have proven to be a powerful tool in many applications and to be robust enough to countervail most differences between simulation and practice, they are not optimal if disturbances in the system data occur. If these controllers are applied in a real process, the possibility of data disturbances force recomputing the feedback control law in real–time to preserve stability and optimality, at least approximately. For this purpose, variations of the classical closed–loop controller with the extention to a trackingtype controller are analysed by means of an industrial application of container cranes. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

An Esterase‐like Lyase Catalyzes Acetate Elimination in Spirotetronate/Spirotetramate Biosynthesis

Spirotetronate and spirotetramate natural products include a multitude of compounds with potent antimicrobial and antitumor activities. Their biosynthesis incorporates many unusual biocatalytic steps, including regio‐ and stereo‐specific modifications, cyclizations promoted by Diels–Alderases, and acetylation‐elimination reactions. Here we focus on the acetate elimination catalyzed by AbyA5, implicated in the formation of the key Diels–Alder substrate to give the spirocyclic system of the antibiotic abyssomicin C. Using synthetic substrate analogues, it is shown that AbyA5 catalyzes stereospecific acetate elimination, establishing the (R)‐tetronate acetate as a biosynthetic intermediate. The X‐ray crystal structure of AbyA5, the first of an acetate‐eliminating enzyme, reveals a deviant acetyl esterase fold. Molecular dynamics simulations and enzyme assays show the use of a His‐Ser dyad to catalyze either elimination or hydrolysis, via disparate mechanisms, under substrate control.     

Volume integrals for low-energy p+208Pb optical potentials

Real and imaginary volume integrals for p+²⁰⁸Pb scattering are determined from sub-Coulomb cross section and analyzing power data. Additional consideration of neutron data yields the real symmetry potential. The results are compared with different theoretical approaches.