Homogenization of random elastic networks with non-affine kinematics

This contribution concerns the mechanics of materials with random network microstructures. It develops a general homogenization approach that allows to link the microscopic deformation of fibers in the disordered network with the macroscopic response of the continuous solid. This link is established by a novel micro-macro relation based on the kinematics of maximal advance paths that constrains the unknown microscopic stretch of fibers with respect to the macroscopic strain. This relation accounts for the topology of the network, in particular, its connectivity and takes for the tetrafunctional networks a clearly interpretable tensorial form. In line with the principle of the minimum averaged free energy the elastic response of the network is obtained by the relaxation of the variable fiber stretch subjected to the kinematic constraint. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Manifold dynamic non-covalent interactions for steering molecular assembly and cyclization

Deciphering rich non-covalent interactions that govern many chemical and biological processes is crucial for the design of drugs and controlling molecular assemblies and their chemical transformations. However, real-space characterization of these weak interactions in complex molecular architectures at the single bond level has been a longstanding challenge. Here, we employed bond-resolved scanning probe microscopy combined with an exhaustive structural search algorithm and quantum chemistry calculations to elucidate multiple non-covalent interactions that control the cohesive molecular clustering of well-designed precursor molecules and their chemical reactions. The presence of two flexible bromo-triphenyl moieties in the precursor leads to the assembly of distinct non-planar dimer and trimer clusters by manifold non-covalent interactions, including hydrogen bonding, halogen bonding, C–H⋯π and lone pair⋯π interactions. The dynamic nature of weak interactions allows for transforming dimers into energetically more favourable trimers as molecular density increases. The formation of trimers also facilitates thermally-triggered intermolecular Ullmann coupling reactions, while the disassembly of dimers favours intramolecular cyclization, as evidenced by bond-resolved imaging of metalorganic intermediates and final products. The richness of manifold non-covalent interactions offers unprecedented opportunities for controlling the assembly of complex molecular architectures and steering on-surface synthesis of quantum nanostructures.

A real-space characterization of dynamic non-covalent interactions in molecular assemblies and chemical reactions at the atomic bond level.     

A new strategy for asymmetric synthesis of aminophosphonic acid derivatives: the first enantioselective catalytic reduction of C-phosphorylated imines

The first highly enantioselective catalytic reduction of 1-imino-2,2,2-trifluoroethylphosphonates and the synthesis of enantiomerically enriched biorelevant phosphonotrifluoroalanine is reported.     

Synthesis of sulfonimide-based dendrimers and dendrons possessing mixed 1 → 2 and 1 → 4 branching motifs

The synthesis of dendrimers and a chlorosulfo-dendron possessing a unique combination of 1?→?2 and 1?→?4 branching types is described. The procedure consists of a two-step preparation of 3,5-dinitrobenzene-1-sulfonyl chloride, which was used for the persulfonylation of p-toluidine and 4-(benzylthio)aniline. The obtained tetranitro compounds were reduced to the corresponding tetraamines. The latter were decorated with eight 4-toluene sulfonyl groups each to furnish the corresponding dendrimers. Oxidation of the dendrimer possessing a 4-(benzylthio)phenylene core with N-chlorosuccinimide resulted in the formation of a dendron with a sulfonyl chloride functionality at the focal point.     

Catalytic activity of Pt-promoted CdS nanocrystals covered with a polymer in photoelectrochemical hydrogen production by water splitting

Photocatalytic properties of Pt-promoted CdS nanocrystals functionalized by the polymer coating were investigated. Deposition of Pt on the surface of the nanoparticles followed by polymer functionalization provides a high photocatalytic activity (1.45 mmol h^–1 mg^–1 at 0.93 W cm^–2) and apparent quantum yield (7%, λ = 445 nm) of the particles. Dependence of the rate of H₂ evolution on Pt loading is described by a curve with the maximum, whereas the quantum yield decreases with an increase in the light flux density. The photocatalytic activity of the nanocrystals increases more than 2 times with polymer coatining.     

Atomic force microscopy investigation of phage infection of bacteria

Atomic force microscopy (AFM) was used to study the process of infection of bacterial cells by bacteriophages, for which purpose experimental protocols were elaborated. Three types of bacteriophages were characterized with AFM and transmission electron microscopy (TEM). Bacteriophage interaction with cells was studied for three bacterial hosts: Gram-negative Escherichia coli 057 and Salmonella enteritidis 89 and Gram-positive Bacillus thuringiensis 393. Depending on the phase of lytic cycle, different cell surface changes are observed in AFM images of infected cells in comparison with intact cells: from phage adsorption on the cells and flagella to complete lysis of the cells, accompanied by the release of a large number of newly formed phages. Control experiments (cells without phages and cells with nonspecific phages) did not reveal any surface changes. Penetration of phages inside obligate aerobe Bacillus thuringiensis was shown to be oxygen-dependent and required aeration in laboratory conditions. Our results show great potential of using AFM for numerous fundamental and applied tasks connected with pathogen-host interaction.     

Chemical catalytic vapor deposition (CCVD) synthesis of carbon nanotubes by decomposition of ethylene on metal (Ni, Co, Fe) nanoparticles

A simple method for producing unsupported nickel catalyst that can be used to synthesize multi-wall carbon nanotubes (MWNT) has been developed. The yield of purified MWNTs is about 1.8 g_mwnt/(g_cat×h).