Tips and Tricks for the Surface Engineering of Well-Ordered Morphologically Driven Silver-Based Nanomaterials

Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface-regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighted.     

DSC analysis of strengthening precipitates in ultrafine Al–Mg–Si alloys

Equal channel angular pressing (ECAP) was carried out on solution annealed samples of Al–Mg–Si–Zr and Al–Mg–Si–Zr–Sc alloys to achieve a substantial grain refinement of the materials. Post ECAP aging was then investigated on the ultrafine grained alloys by DSC and TEM analyses. DSC scans were carried out with heating rates ranging from 5 to 30°C min^–1. Peak identification was performed by the support of literature information and TEM analyses. Precipitation kinetics revealed to be similar for both alloys but the Sc-free alloy showed a recrystallization peak at temperatures ranging from 310 to 340°C, depending on the strain accumulated during ECAP. On the contrary, the Sc-containing alloy showed a greater grain stability. Analyses of peak positions and of activation energies as a function of ECAP passes experienced by the samples revealed large modifications of precipitation kinetics in the ultrafine-grained alloys with respect to the coarse-grained materials.     

Optimal Control in Heterogeneous Domain Decomposition Methods for Advection-Diffusion Equations

New domain decomposition methods (DDM) based on optimal control approach are introduced for the coupling of first and second order equations on overlapping subdomains. Several cost functionals and control functions are proposed. Uniqueness and existence results are proved for the coupled problem, and the convergence of iterative processes is analyzed. The work was supported by the Russian Foundation for Basic Research (04-01-00615) and it was partly carried out while the first author was visiting the IACS at EPFL.     

Some properties of multi-degree-of-freedom potential systems and application to statistical equivalent non-linearization

This paper presents some properties of two restricted classes of multi-degree-of-freedom potential systems subjected to Gaussian white-noise excitations. Specifically, potential systems which exhibit damping terms with energy-dependent polynomial form are referred to. In this context, first systems with coupled stiffness terms and damping terms depending on the total energy are investigated. Then, systems with uncoupled stiffness terms and damping terms depending on the total energy in each degree-of-freedom are considered. For these two classes, it is found that algebraic relations among the stationary statistical moments of the energy functions can be derived by applying standard tools of Itô calculus. Further, it is noted that these relations are very useful within the framework of an equivalent statistical non-linearization technique to build approximate solutions for arbitrary non-linear systems.     

Effects of neutron skin on the excitation of isovector modes of neutron-rich nuclei

The existence of a neutron skin in neutron-rich nuclei is discussed in connection with the excitation of isovector dipole and quadrupole giant modes via isoscalar nuclear probes. In the case of large neutron excess, important contributions are obtained from the nuclear excitation, which may even become predominant according to proper kinematical conditions. At variance with the usual situation encountered in inelastic processes, constructive interference can be found between nuclear and Coulomb contributions.     

Ageing of wet-synthesized oxide powders

Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original sintering properties can be recovered after washing the aged powders with ethanol in a basic medium.     

A Formal Total Synthesis of (+)-Methyl Trachyloban-18-oate and (+)-Methyl 16-Oxo-17-norkauran-18-oate: Regio- and Diastereoselective Preparation of Methyl (13S)-13-Hydroxyisoatisiren-18-oate from (−)-Abietic Acid

A novel preparation of methyl (13S)-13-hydroxyisoatisiren-18-oate ( 4 ), a key-intermediate in a synthesis of (+)-methyl trachyloban-18-oate ((+)- 1 ), from (?)-abietic acid, is described. Since (?)- 1 has been previously converted into (?)-methyl 16-oxo-17-norkauran-18-oate ((?)- 16 ), our preparation of 4 constitutes also a formal total synthesis, from (?)-abietic acid, of (+)- 16 . Key steps in this approach were the allene photoaddition to podocarp-8(14)-en-13-one ( 5 ) and the conversion of the endo-toluene-4-sulfonate 11 into the exo-benzoate 12b .     

Structure-based optimization of a non-beta-lactam lead results in inhibitors that do not up-regulate beta-lactamase expression in cell culture

Bacterial expression of beta-lactamases is the most widespread resistance mechanism to beta-lactam antibiotics, such as penicillins and cephalosporins. There is a pressing need for novel, non-beta-lactam inhibitors of these enzymes. One previously discovered novel inhibitor of the beta-lactamase AmpC, compound 1, has several favorable properties: it is chemically dissimilar to beta-lactams and is a noncovalent, competitive inhibitor of the enzyme. However, at 26 microM its activity is modest. Using the X-ray structure of the AmpC/1 complex as a template, 14 analogues were designed and synthesized. The most active of these, compound 10, had a K(i) of 1 microM, 26-fold better than the lead. To understand the origins of this improved activity, the structures of AmpC in complex with compound 10 and an analogue, compound 11, were determined by X-ray crystallography to 1.97 and 1.96 A, respectively. Compound 10 was active in cell culture, reversing resistance to the third generation cephalosporin ceftazidime in bacterial pathogens expressing AmpC. In contrast to beta-lactam-based inhibitors clavulanate and cefoxitin, compound 10 did not up-regulate beta-lactamase expression in cell culture but simply inhibited the enzyme expressed by the resistant bacteria. Its escape from this resistance mechanism derives from its dissimilarity to beta-lactam antibiotics.     

Palladium-arene interactions in catalytic intermediates: an experimental and theoretical investigation of the soft rearrangement between eta1 and eta2 coordination modes

A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl]2*CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C(ipso) atom of the arene lies almost at the fourth planar coordination site of the metal [Pd-C(ipso) = 2.22(1) A (average)], and due to the arene's tilting, the substituted C(ortho) atom is relatively close to the metal atom [2.54(1) A (average)]. The coordinated C(ipso)-C(ortho) linkage, in a seemingly dihapto coordination, is anti with respect to the CH2 bridge of the bicycloheptyl unit. Variable-temperature NMR experiments for the para-substituted dimer 9 reveal restricted rotation of the two aryl groups about the corresponding C-C(ipso) bonds (DeltaE < or =17 kcal x mol(-1)). DFT-B3LYP calculations have been carried out on the known and similar monomer (phenylbicycloheptenyl)Pd(PPh3)I (4) and its related substituted derivatives. The essential results are as follows: (i) The potential energy surface for twisting the phenyl ring away from the symmetric eta(1) coordination in 4 is very flat (DeltaE < or = 1 kcal x mol(-1)) whereas an Atoms in Molecules analysis excludes the existence of an actual Pd-C(ortho) bond in the seemingly eta2-type conformer. (ii) Complete rotation of the unsubstituted phenyl ring is not facile but feasible. A significant strain affects the transition-state structure featuring a Pd-HC(aryl) agostic-type bond. The calculated destabilization of 10.3 kcal x mol(-1), with respect to the ground state, can be compared to the experimental barrier of the dimer 9. (iii) Various methyl-substituted derivatives of 4 have been optimized, and their structural and energetic trends are discussed. An almost ideal eta1 coordination is shown by the anti conformer of the C(ortho)-substituted complex due steric effects. For all of the other cases, a slipped eta2 coordination may be described. As a general conclusion, the unsaturated metal center receives pi electron density of the arene mainly through its C(ipso) atom. The effect may be slightly improved if the C(ortho) atom also gets closer to the metal, but in no case, does the slipped eta2 coordination seem to be crucial for the stability of the system.