Three Reactions,One Catalyst: A Multi-Purpose Platinum(IV) Complex and its Silica-Supported Homologue for Environmentally Friendly Processes

Although platinum nanoparticles and complexes -especially of Pt(0) and Pt(II)- are well known catalysts, siloxane-based platinum complexes are rarely reported. Herein, a Platinum(IV) complex of 4-aminopyridinium-modified disiloxane was prepared and characterized by medium and far infrared spectroscopy, NMR and EDX. The formation of the complex was monitored by UV–Vis spectroscopy, which showed the high affinity and selectivity of this ligand for Pt, with a stability constant of 7.53·10³ M⁻¹. The catalytic activity of the siloxane-based complex was tested in three types of reactions: reduction of p-nitrophenol, oxidation of glucose and starch, and hydrosilylation. The hydrophobic behavior of the permethylated disiloxane moiety ensures good hydrolytic stability, while the N-donor ligand stabilizes the in-situ formed Pt nanoparticles. The generation of Pt nanoparticles during p-nitrophenol reduction was confirmed by TEM and SEM. Contrary to most reports, the aerobic oxidation of mono- and polysaccharides occurred without oxidation agents or mediators added, in mild conditions, at room temperature and pH ~9. The same metal complex was found active in hydrosilylation of vinyl-siloxanes with temperature-modulated rate, thus being useful in silicone cross-linking systems without the need of inhibitors. The method was adapted to one-pot synthesis of silica-supported Pt(IV) complex, which acted as efficient and reusable heterogeneous hydrosilylation catalyst, limiting the contamination of the product with Pt. This approach is promising for superior valorization of scarcely available and expensive platinum metal. By the same method, multifunctional soluble complexes and mesoporous silica may be obtained, with tunable catalytic performance.     

Base-Assisted Imidization: A Synthetic Method for the Introduction of Bulky Imide Substituents to Control Packing and Optical Properties of Naphthalene and Perylene Imides

We report the direct imidization of naphthalene and perylene dicarboxylic anhydrides/esters with bulky ortho,ortho-diaryl- and ortho,ortho-dialkynylaniline derivatives. This imidization method uses n-butyllithium as a strong base to increase the reactivity of bulky amine derivatives, proceeds under mild reaction conditions, requires only stoichiometric amounts of reactants and gives straightforward access to new sterically crowded rylene dicarboximides. Mechanistic investigations suggest an isoimide as intermediary product, which was converted to the corresponding imide upon addition of an aqueous base. Single-crystal X-ray diffraction analyses reveal dimeric packing motifs for monoimides, while two-side shielded bisimides crystallize in isolated molecules without close π–π-interactions. Spectroscopic investigations disclose the influence of the bulky substituents on the optical properties in the solid state.     

Histamine detection using functionalized porphyrin as electrochemical mediator

This study reports on deposition of asymmetrical substituted meso-phenyl porphyrin, 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin (CPTPP) thin films by matrix-assisted pulsed laser evaporation (MAPLE) on screen-printed electrodes, aiming for histamine detection. Raman spectrometry confirmed that CPTPP chemical structure was preserved in MAPLE-deposited thin films at 200 mJ/cm² laser fluence. Atomic force microscopy topography revealed that MAPLE-deposited thin films have a better coverage on the working electrode made of carbon compared to the ones obtained by dropcasting. Cyclic voltammetry demonstrated that CPTPP is an appropriate mediator for histamine detection in trichloroacetic acid solution. We proved that MAPLE serves as a soft technique in fabrication of porphyrin thin films and patterns.     

Uniformly complete quotient space

The uniformly complete quotient space of a locally compact group is introduced. It is shown that the operator space dual is a completely contractive Banach algebra, which contains the completely bounded Fourier multiplier algebra as a completely contractively complemented Banach subalgebra. A natural completely isometric representation of on is studied and some equivalent amenability conditions associated with are proved.

     

Balancing Donor-Acceptor and Dispersion Effects in Heavy Main Group Element π Interactions: Effect of Substituents on the Pnictogen⋅⋅⋅π Arene Interaction

High-level ab initio calculations using the DLPNO-CCSD(T) method in conjunction with the local energy decomposition (LED) were performed to investigate the nature of the intermolecular interaction in bismuth trichloride adducts with π arene systems. Special emphasis was put on the effect of substituents in the aromatic ring. For this purpose, benzene derivatives with one or three substituents (R=NO₂, CF₃, OCHO, OH, and NH₂) were chosen and their influence on donor-acceptor interaction as well as on the overall interaction strength was examined. Local energy decomposition was performed to gain deeper insight into the composition of the interaction. Additionally, the study was extended to the intermolecular adducts of arsenic and antimony trichloride with benzene derivatives having one substituent (R=NO₂ and NH₂) in order to rationalize trends in the periodic table. The analysis of natural charges and frontier molecular orbitals shows that donor-acceptor interactions are of π→σ* type and that their strength correlates with charge transfer and orbital energy differences. An analysis of different bonding motifs (Bi⋅⋅⋅π arene, Bi⋅⋅⋅R, and Cl⋅⋅⋅π arene) shows that if dispersion and donor-acceptor interaction coincide as the donor highest occupied molecular orbital (HOMO) of the arene is delocalized over the π system, the M⋅⋅⋅π arene motif is preferred. If the donor HOMO is localized on the substituent, R⋅⋅⋅π arene bonding motifs are preferred. The Cl⋅⋅⋅π arene bonding motif is the least favorable with the lowest overall interaction energy.     

Phospholipid bilayers as biomembrane-like barriers in layer-by-layer polyelectrolyte films

Dipalmitoylphosphatidylcholine (DPPC) bilayer was created on the surface of an exponentially growing poly(glutamic acid)/poly(lysine) (PGA/PLL) layer-by-layer polyelectrolyte film. The lipid bilayer decreased the surface roughness of the polyelectrolyte film. The layer-by-layer construction of the polyelectrolyte film could be continued on the top of the DPPC layer. The lipid bilayer, however, formed a barrier in the interior of the polyelectrolyte film, which blocked the diffusion (a prerequisite for exponential growth) of the polyelectrolytes. Thus, a new growth regime started in the upper part of the polyelectrolyte film, which was added to embed the DPPC bilayer. The structure and the dynamics of the DPPC bilayer on the polyelectrolyte film surface remained similar to that of its hydrated multibilayers, except that the phase transition became wider. In the case of embedded DPPC bilayers, in addition, the phase-transition temperature also decreased. This is the result of interactions with the nonconcerted movements of the barrier-separated lower and higher parts of the polyelectrolyte film. Gramicidin A (GRA) as a model of lipid-soluble peptides and proteins was successfully incorporated into such DPPC films. The DPPC films, either with or without GRA, were remarkably stable; as many heating-cooling cycles to measure phase transition could be carried out without visible alterations as wanted.     

Modified Kantorovich operators with better approximation properties

Numerical Algorithms - In the present paper, we study a new kind of Bernstein-Kantorovich-type operators. Here, we discuss a uniform convergence estimate for this modified form. Also, some direct...     

Fundamental studies of intense heavy-ion beam interaction with solid targets

Intense (10/sup 11/ particles/1 /spl mu/s /spl sim/300 MeV/u) heavy ion beams are generated in the heavy-ion synchrotron (SIS) of the GSI-Darmstadt facility. Large volumes of strongly coupled plasmas are produced by heavy ion beam interaction with solid targets, with plasma densities close to the solid state, pressures of about 100 kbar, and temperatures of up to 1 eV, with relevance for equation of state (EOS) of matter, astrophysics, and low-entropy shock compression of solids. The plasmas created by ion beam interaction with metallic converters and cryogenic crystals were studied by backlighting shadowgraphy and by time-resolved spectroscopy in the visible and vacuum ultraviolet ranges. Low entropy weak shock waves induced by the ion beams in the metal-plexiglass multilayered targets were visualized by time resolved schlieren measurements, revealing induced multiple shockwaves with pressures higher than 15 kbar in a plexiglass window and propagation velocities up to 35% higher than the speed of sound in plexiglass at room temperature. To get an insight into the plasma dynamics, both types of experiments are simulated by the BIG-2 two-dimensional hydrodynamic code.